Polymerization method and polymers formed therewith

ABSTRACT

Condensation of fluoro-substituted and silyl-substituted monomers provides polymers suitable for use, e.g., as engineering polymers. A monomer composition is condensed in the presence of a basic catalyst. The monomer composition contains a compound of formula F—X—F and a compound of formula (R 1 )3Si—Z—Si(R 1 )3, and forms an alternating X—Z polymer chain and a silyl fluoride byproduct. X has the formula -A(-R 2 -A)n-; each A is SO 2 , C(═O), or Het; R 2  is an organic moiety; n is 0 or 1; Het is an aromatic nitrogen heterocycle; Z has the formula -L-R 3 -L-; each L is O, S, or N(R 4 ); and each R 3  is an organic moiety, and R 4  comprises H or an organic moiety.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 61/732,727, filed on Dec. 3, 2012, which is incorporated herein byreference in its entirety.

GOVERNMENT SUPPORT

This invention was made with government support from National Institutesof Health, Grant No. GM-087620, and National Science Foundation, GrantNo. CHE-0848982. The United States government has certain rights in thisinvention.

FIELD OF THE INVENTION

The present invention relates to polymers and methods of producingpolymers. More particularly, the invention relates to methods ofproducing polymers via condensation of fluorinated and silylatedmonomers in the presence of a basic catalyst, and polymers obtainable bythe methods.

BACKGROUND

Polymeric materials play an important role in modern materials science.Synthetic condensation polymers (e.g., materials having organosulfone,organosulfate, organocarbonate, organocarbamate, organourea, or organicester-type polymeric backbones) are utilized in a variety of productsand industries, including, for example, packaging, high performanceengineering materials, medical prostheses and implants, optics, andconsumer plastic goods. There is an ongoing need for new methods ofpreparing polymeric materials, particularly solid polymers (e.g.,plastics), including materials for high value, specialty applications(e.g., medical prostheses and implants, engineering materials, oroptics). The polymerization methods and polymers described hereinaddress these needs.

A handful of reactions are at the core of multimillion-ton polymerindustry. Most commodity polymers are synthesized from olefins byforming carbon-carbon backbones, whereas engineering polymers arecommonly prepared via condensation reactions of monomers containing anactivated carbonyl group or its equivalent and a suitable nucleophile,thus forming carbon-heteroatom linkages. Polyesters, polyamides,polyurethanes, and polyimides are produced in this manner. Despite thevariety of backbone structures, polymers containing sulfur(VI) “—SO₂-”connectors are virtually absent from the literature and barely used inindustrial applications, with the exception of polysulfones, in whichthe sulfone group is already present in the monomers (see e.g.,Garbassi, in Kirk-Othmer Encyclopedia of Chemical Technology; FifthEdition; John Wiley & Sons: 2007; Vol. 10).

Unsurprisingly, most reported attempts to synthesizesulfur(VI)-containing polymers relied on reactions mimicking carbonylgroup-based condensations, i.e. reactions of sulfonyl chlorides withnucleophiles (see e.g., (a) Goldberg et al., U.S. Pat. No. 3,236,808;(b) Firth, U.S. Pat. No. 3,895,045; (c) Thomson et al., J. Pol. Sci.,Part A 1964, 2: 1051; (d) Worket et al., Polym. Sci., Part A: Polym.Chem. 1968, 6: 2022; (e) Schlott et al., in Addition and CondensationPolymerization Processes; American Chemical Society: 1969; 91:703-716)and, to a much lesser extent, Friedel-Crafts sulfonylations (see e.g.,Cudby et al., Polymer 1965, 6:589). Despite the attractive properties ofpolymers obtained by those methods, such as good thermal and hydrolyticstability and mechanical resilience (see Thompson et al., id.; Worket etal., id.; and Schlott et al., id.), the unselective reactivity ofsulfur(VI) chlorides, which are susceptible to hydrolysis andparticipate in facile redox transformations, especially chlorinations,significantly limit utility of these methods and materials.

Reactions of many silylated and fluorinated compounds are known inorganic synthesis and also in polymer chemistry. In 1983, Kricheldorfintroduced the “silyl method” for the synthesis of polyaryl ethers,taking advantage of the strength of the Si—F bond and the innocuousnature of the silyl fluoride byproducts (Kricheldorf et al., J. Pol.Sci.: Pol. Chem. Ed. 1983, 21:2283; Bier et al., U.S. Pat. No.4,474,932). In 2008, Gembus demonstrated that sulfonyl fluorides(R—SO₂F) react with silyl ethers in the presence of a catalytic amountof DBU, producing aryl sulfonates (Gembus et al., Synlett. 2008, 1463).

Sulfur(VI) fluorides, in particular sulfuryl fluoride (SO₂F₂) and itsmonofluorinated derivatives, sulfonyl (RSO₂—F) fluorides, sulfamoyl(R₂NSO₂—F) fluorides, and fluorosulfates (ROSO₂—F), in which R is anorganic moiety, stand in stark contrast to other sulfur(VI) halides.These sulfur oxofluorides are much more hydrolytically stable, redoxsilent, and do not act as halogenating agents. Nevertheless, theirselective reactivity can be revealed when an appropriate nucleophile ispresented under the right conditions. In the early 1970s, Firth preparedpoly(arylsulfate)bisphenol A (BPA) polymers from fluorosulfates of BPA(obtained from BPA and SO₂F₂), and disodium salts of bisphenols (see,e.g., Firth, J. Pol. Sci., Part B 1972, 10:637; and Firth, U.S. Pat. No.3,733,304). The polymerization required prolonged heating and produced asignificant quantity of byproduct (12 to 22%) which Firth indicated tobe cyclic oligomers. Removal of the byproduct required repeatedprecipitation of the polymer from dimethylformamide (DMF) into methanol.

There is an ongoing need for new polymerization methods that areversatile and capable of producing a wide variety of polymer structures,including materials formally considered to be condensation polymers,under relatively mild and scalable conditions. There also is a need fornew polymers, e.g., for structural, packaging, and fiber applications,and for polymers from processes that tolerate monomers bearing extra,non-interfering groups, which can be functionalized for specialtyapplications. The methods and polymer described herein address theseneeds. In addition to providing a practical route to polymers withuseful properties, the exceptionally facile synthesis of organosulfatesdescribed herein highlights the underappreciated potential of thesulfate connector, in particular, in organic chemistry, as well asunique reactivity features of sulfur(VI) oxofluorides. The polymers andmethods described herein should find immediate applications acrossdifferent disciplines.

SUMMARY

Polymerization methods described herein provide a straightforwardsynthesis of relatively high molecular weight polymers by catalyzedpolymerization of activated fluoro-substituted and silyl-substitutedmonomers under mild reaction conditions. Polymers with surprisingly highmolecular weights are achieved under unexpectedly robust conditions ofstoichiometry, temperature, and solvent environment. Fluorosulfate,fluorosulfonate, carbonyl fluoride, and certain heterocyclic fluoridemonomers react with silyl ether, silyl amine (particularly with C(═O)Fmonomers), and silyl sulfide monomers under mild conditions to form awide variety of polymeric materials, including, e.g., polysulfates,polycarbonates, polysulfonates and related materials. The selectivity ofthe present method is demonstrated by the successful formation ofpolymers and copolymers containing technologically useful buildingblocks found in many packaging and engineering polymers. In onepreferred embodiment, polysulfate polymers are prepared from arylbis-fluorosulfates and aryl bis-silyl ethers under mild reactionsconditions, which are amenable to bulk (i.e., solvent-free)polymerization. The polymer can be substantially linear or in someembodiments can include or consist of cyclic polymer chains in which theend groups of a single polymer chain have bonded together to form alarge ring.

A monomer composition containing fluoro-substituted andsilyl-substituted monomers is condensed in the presence of a basiccatalyst to form a polymer chain and a silyl fluoride byproduct that isreadily separable from the polymer product. The monomer compositioncomprises at least one compound of formula F—X—F and at least onecompound of formula (R¹)₃Si—Z—Si(R¹)₃. Each R¹ independently is ahydrocarbyl group; X has the formula -A(-R²-A)n-; each A independentlyis SO₂, C(═O), or Het, preferably SO₂; R² comprises a first organicmoiety; n is 0 or 1; Het is an aromatic heterocycle comprising at leasttwo carbon atoms and at least one nitrogen atom in a heteroaromatic ringthereof (preferably 1,3,5-triazine), and when A is Het, the Fsubstituent is attached to a carbon atom of the heteroaromatic ringthereof; Z has the formula -L-R³-L-; each L independently is O, S, orN(R⁴), preferably O; R³ comprises a second organic moiety, and R³preferably comprises at least one aryl or heteroaryl moiety; each Lgroup preferably is directly bonded to an aryl or heteroaryl moiety ofR³; and each R⁴ independently is H or a third organic moiety.Alternatively, the monomer composition can comprise at least onecompound of formula F—X—Z—Si(R¹)₃ in addition to, or in place of, thecombination of F—X—F and (R¹)₃Si—Z—Si(R¹)₃.

During polymerization, the respective A and L groups of the monomerstogether form an X—Z polymer chain, and the F and (R¹)₃Si substituentsform a silyl fluoride byproduct of formula (R¹)₃Si—F, which is readyseparable from the polymer product and can be recycled. In preferredembodiments, the polymers include relatively stable fluoro-substitutedend groups, which can be modified under selective reaction conditions,if desired. The basic catalyst can be an amidine, a guanidine, aphosphazene, a nitrogen-heterocyclic carbene, a tertiary alkoxide, afluoride salt, or a combination of two or more of the foregoing.Surprisingly, the mixtures of the bis-silyl and bis-fluoro monomers areunreactive, even at elevated temperatures, in the absence of the basiccatalyst.

The polymerization methods are particularly useful for preparing arylpolysulfates, such as bisphenol polysulfates, under mild, high yieldingconditions, to afford polymers with molecular weights and physicalproperties suitable for e.g., materials applications such as engineeringmaterials, packaging materials, and the like. One advantage of thepolymers produced by the methods described herein, including the arylpolysulfates, is that in many cases the end groups of the polymersinclude fluoro groups that can be separately reacted to functionalizethe ends of the polymer chains in a manner not readily achievable byprior methods. In the case of the aryl polysulfates, the —OSO₂F and—SO₂F end groups are surprisingly stable, but can be selectively coaxedinto reactions with phenolic OH groups and amino groups or hydrolyzed to—OH and —SO₃ ⁻ groups, respectively, under readily controllableconditions, as described herein.

The silyl fluoride byproduct can be recycled by reaction with a salt(e.g., a sodium or potassium salt) of a phenolic monomer precursor(e.g., bisphenol A) to form a useful bis-silylated monomer (e.g., abis-silyl bisphenol A) and a fluoride salt (e.g., sodium fluoride). Thebis-silylated monomer can be utilized in another polymerizationreaction.

One embodiment of the polymerization method described herein involvesreacting a bis-fluorinated first monomer with a bis-silylated secondmonomer in the presence of a basic catalyst to form a polymer chain anda silyl fluoride byproduct. The fluoro substituents of the first monomerare attached to an electron deficient group such as a sulfonyl, carbonylor heteroaryl activating group (preferably sulfonyl), and the silylsubstituents of the second monomer are linked to an organic core moietyvia an oxygen, sulfur, or nitrogen atom (preferably an oxygen atom).When the first and second monomers are combined with the catalyst, thefluoride substituents of the first monomer react with the silylsubstituents of the second monomer to form a silyl fluoride, and theelectron deficient activating groups of the first monomer condense withthe linking atoms of the second monomer to form a polymer chain. Thefirst monomer optionally can include an organic core group, as well.

In some embodiments, the method comprises the step of reacting a firstmonomer composition comprising at least one compound of formula F—X—F(preferably FSO₂F) with a second monomer composition comprising at leastone compound of formula (R¹)₃Si—Z—Si(R¹)₃, in the presence of a basiccatalyst, to form an alternating X—Z polymer chain and a silyl fluoridebyproduct of formula (R¹)₃Si—F. The X portion of the first monomer hasthe formula -A(-R²-A)n-, wherein each A independently is SO₂, C(═O), orHet, preferably SO₂; R² comprises a first organic moiety; n is 0 or 1;and Het is an aromatic heterocycle comprising at least two carbon atomsand at least one nitrogen atom in a heteroaromatic ring thereof(preferably a 1,3,5-triazine), in which each F is attached to a carbonatom of the heteroaromatic ring. Each R¹ of the second monomerindependently is a hydrocarbyl group (e.g., linear or branched alkyl,phenyl, and the like); Z has the formula -L-R³-L-, wherein each Lindependently is O, S, or N(R⁴), preferably O; R³ comprises a secondorganic moiety and R³ preferably comprises at least one aryl orheteroaryl moiety; each L group preferably is directly bonded to an arylor heteroaryl moiety of R³; and R⁴ is H or a third organic moiety.During polymerization, the respective F and (R¹)₃Si substituents of thefirst and second monomers form the silyl fluoride, while the respectiveA and L groups of the first and second monomers alternately condense toform the alternating X—Z polymer chain. When n is 0, each F substituentof the first monomer is attached to the same A group.

The basic catalyst used in the polymerization methods described hereincomprises at least one material selected from the group consisting of anamidine, a guanidine, a phosphazene, a nitrogen-heterocyclic(N-heterocyclic) carbene, a tertiary alkoxide, and a fluoride salt. Forexample, the basic catalyst can comprise an amidine base (e.g.,1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and the like), a guanidine(e.g., 1,1,3,3-tetramethylguanidine (TMG),1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene (MTBD) and the like), aphosphazene base (e.g.,2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine(BEMP),1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ⁵,4λ⁵-catenadi(phosphazene)(P₄-t-Bu), and the like), a nitrogen-heterocyclic carbene (e.g., animidazole-2-ylidene, a 1,2,4-triazole-5-ylidene, a thiazole-2-ylidene,an imidazolin-2-ylidene, and the like), a tertiary alkoxide (e.g.,potassium tert-butoxide and the like), or a fluoride-containing salt(e.g., CsF, CsFHF, KF, tetrabutylammonium fluoride (TBAF),tris(dimethylamino)sulfonium-difluorotrimethylsilicate (TASF), and thelike), or a combination of two or more thereof. Preferably, the basecomprises an amidine, a phosphazene, or both. If desired, a combinationof catalysts can be added as a mixture or sequentially.

Preferably, the first and second monomers are reacted in approximatelyequimolar amounts or with an excess (e.g., 0.01 up to about 10 mol %excess) of the first (i.e., fluorinated) monomer. The first and secondmonomers can be contacted with one another in neat (solventless or bulk)form, or in a solvent (e.g., a halogenated hydrocarbon, acetonitrile,pyridine, N-methylpyrrolidone, and the like), a combination of solvents(e.g., together or sequentially added), or a combination of solventlessand solvent conditions (e.g., sequentially). Typically, thepolymerization is performed at a temperature in the range of about 20 toabout 200° C. for about 0.5 to about 48 hours. The polymerizationreaction is surprisingly facile, and typically exhibits a relativelymodest heat of reaction. Additionally, the reaction conditions andmonomers are surprisingly tolerant of a large variety of organicmoieties and substituents. This translates into an unprecedented freedomof selection of “AA” and “BB” monomer components, including groups thatare known to interfere with normal acid-base reactions, and the abilityto tailor the functionality of the resulting polymer to a very highdegree.

The first monomer can be a single compound conforming to the formulaF—X—F or a mixture of compounds having different X groups. Similarly,the second monomer may be a single compound conforming to the formula(R¹)₃Si—Z—Si(R¹)₃ or a mixture of compounds having different R¹ groups,Z groups, or both. Such mixtures of monomers can be formulated in anydesired proportion and with any desired X and Z groups to impart desiredproperties to the resulting polymer, such as a desired molecular weight,a desired molecular weight distribution, desirable physical ormechanical properties (e.g., glass transition temperature, hydrolyticstability, tensile strength, impact resistance, ductility, resilience,plasticity, and the like), or biodegradability, for example.

In one embodiment, the first monomer has the formula F-A-F. In thisembodiment, the first monomer can be, for example, FSO₂F, FC(O)F, orF-Het-F (preferably FSO₂F). As described herein, Het is an aromaticheterocycle comprising at least two carbon atoms and at least onenitrogen atom in a heteroaromatic ring thereof, in which each F isattached to a carbon atom of the heteroaromatic ring. An exemplaryheterocycle is 1,3,5-triazine, and the F substituents are covalentlybonded to a carbon atom at two or more of positions 2, 4, and 6. When agaseous monomer such as FSO₂F is utilized, the reaction can be performedin a reactor capable of operating at pressures greater that oneatmosphere, if desired.

In other embodiments, the first monomer is a material of formulaF-A-R²-A-F. R² is a first organic moiety, which can comprise or consistof an organic core material, such as a hydrocarbon, a heterocycle, acarbohydrate, an amino acid, a polypeptide, a peptide analog, and thelike, or any combination of two or more thereof, while the A groups areselected from sulfonyl, carbonyl, or heteroaryl (Het), preferably SO₂,as described above. In some embodiments, R² can be represented by theformula -L¹-R-L¹-, in which each L¹ independently is selected from thegroup consisting of O, S, and N(R⁴), preferably O; each R⁵ independentlycomprises the first organic moiety: and each R⁴ independently comprisesH or a third organic moiety. Alternatively, or in addition, R² can berepresented by the formula -L¹-R⁵—, in which each L¹ and R⁵ are asdefined above.

A polymer produced by the present methods comprises a polymer chain thatcan be represented by Formula (I): (-A(-R²-A)n-L-R³-L)x-, in which eachA independently is SO₂, C(═O), or Het, preferably SO₂; each R²independently comprises the first organic moiety; each n independentlyis 0 or 1; each Het independently is an aromatic heterocycle comprisingat least two carbon atoms and at least one nitrogen atom in aheteroaromatic ring thereof; each L independently is O, S, or N(R⁴),preferably O; each R³ comprises a second organic moiety and R³preferably comprises at least one aryl or heteroaryl moiety; each Lgroup preferably is directly bonded to an aryl or heteroaryl moiety ofR³; each R⁴ independently is H or a third organic moiety; and x is theaverage number of repeating units in the polymer and has a value of atleast 10 (e.g., 10 to 100,000 or more). The polymer chain includes atleast one end group that is derived from the first monomer, i.e., an endgroup including a moiety of formula E-A-, such as E-A(-R²-A)n-, in whichE preferably is a fluoro substituent (F), or E is a functional groupobtainable by nucleophilic displacement of F from the “A” moiety, suchas azido, amino, alkylamino, arylamino, alkoxy, aryloxy, alkylthio, andsimilar groups. In some embodiments, E is selected from fluoro, OR⁸,NHR⁸, N(R⁸)₂, azido, CN, or SR⁸, and each R⁸ independently is an organicmoiety. When A is Het, each L group is attached to a carbon atom of theheteroaromatic ring thereof.

Alternatively, or in addition, the polymer includes a polymer chain thatcan be represented by Formula (II): (-A-R²-A-L-R³-L)y-, wherein each Aindependently is SO₂, C(═O), or Het, preferably SO₂; each R²independently comprises the first organic moiety; each Het independentlyis an aromatic heterocycle comprising at least two carbon atoms and atleast one nitrogen atom in a heteroaromatic ring thereof (preferably1,3,5-triazine); each L independently is O, S, or N(R⁴), preferably O;each R³ comprises a second organic moiety and R³ preferably comprises atleast one aryl or heteroaryl moiety; each L group preferably is directlybonded to an aryl or heteroaryl moiety of R³; each R⁴ independently is Hor a third organic moiety; and y is the average number of repeatingunits in the polymer and has a value of at least 10 (e.g., 10 to 100,000or more). The polymer chain includes at least one end group that isderived from the first monomer, i.e., an end group including a moiety offormula E-A-, such as E-A-R²-A-, in which E preferably is a fluorosubstituent (F), or E is a functional group obtainable by nucleophilicdisplacement of F from the “A” moiety, such as azido, amino, alkylamino,arylamino, alkoxy, aryloxy, alkylthio, and similar groups. In someembodiments, E is selected from fluoro, OR⁸, NHR⁸, N(R⁸)₂, azido, CN, orSR⁸, and each R⁸ independently is an organic moiety. When A is Het, eachL group is attached to a carbon atom of the heteroaromatic ring thereof.

In some other embodiments, the polymer includes a polymer chain that canbe represented by Formula (III): (-A-L¹-R⁵-L¹-A-L-R³-L)z-, wherein eachA independently is SO₂, C(═O), or Het, preferably SO₂; each R⁵independently comprises the first organic moiety; each Het independentlyis an aromatic heterocycle comprising at least two carbon atoms and atleast one nitrogen atom in a heteroaromatic ring thereof, preferably1,3,5-triazine; each L and L¹ independently is O, S, or N(R⁴),preferably O; each R³ comprises a second organic moiety and R³preferably comprises at least one aryl or heteroaryl moiety; each Lgroup preferably is directly bonded to an aryl or heteroaryl moiety ofR³; each R⁴ independently is H or a third organic moiety; and z is theaverage number of repeating units in the polymer and has a value of atleast 10 (e.g., 10 to 100,000 or more). The polymer chain includes atleast one end group that is derived from the first monomer, i.e., an endgroup including a moiety of formula E-A-, such as E-A-L¹-R⁵-L¹-A-, inwhich E preferably is a fluoro substituent (F), or E is a functionalgroup obtainable by nucleophilic displacement of F from the “A” moiety,such as azido, amino, alkylamino, arylamino, alkoxy, aryloxy, alkylthio,and similar groups. In some embodiments, E is selected from fluoro, OR⁸,NHR⁸, N(R⁸)₂, azido, CN, or SR⁸, and each R⁸ independently is an organicmoiety. When A is Het, each L and L¹ group is attached to a carbon atomof the heteroaromatic ring thereof.

In yet other embodiments, the polymer includes a polymer chain that canbe represented by Formula (IV): (-A-L¹-R-A-L-R³-L)m-, wherein each Aindependently is SO₂, C(═O), or Het, preferably SO₂; each R⁵independently comprises a first organic moiety; each Het independentlyis an aromatic heterocycle comprising at least two carbon atoms and atleast one nitrogen atom in a heteroaromatic ring thereof; each L and L¹independently is O, S, or N(R⁴), preferably O; each R³ comprises asecond organic moiety and R³ preferably comprises at least one aryl orheteroaryl moiety; each L group preferably is directly bonded to an arylor heteroaryl moiety of R³; each R⁴ independently is H or a thirdorganic moiety; and m is the average number of repeating units in thepolymer and has a value of at least 10 (e.g., 10 to 100,000 or more).The polymer chain includes at least one end group that is derived fromthe first monomer, i.e., an end group including a moiety of formulaE-A-, such as E-A-L¹-R⁵-A-, in which E preferably is a fluorosubstituent (F), or E is a functional group obtainable by nucleophilicdisplacement of F from the “A” moiety, such as azido, amino, alkylamino,arylamino, alkoxy, aryloxy, alkylthio, and similar groups. In someembodiments, E is selected from fluoro, OR⁸, NHR⁸, N(R⁸)₂, azido, CN, orSR⁸, and each R⁸ independently is an organic moiety. When A is Het(e.g., 1,3,5-triazine), each L and L¹ group is attached to a carbon atomof the heteroaromatic ring thereof.

In some other embodiments, the polymer includes a polymer chain that canbe represented by Formula (V): (-A-L-R³-L)p-, wherein each Aindependently is SO₂, C(═O), or Het, preferably SO₂; each Hetindependently is an aromatic heterocycle comprising at least two carbonatoms and at least one nitrogen atom in a heteroaromatic ring thereof;each L independently is O, S, or N(R⁴), preferably O; each R³ comprisesa second organic moiety and R³ preferably comprises at least one aryl orheteroaryl moiety; each L group preferably is directly bonded to an arylor heteroaryl moiety of R³; each R⁴ is H or another organic moiety; andp is the average number of repeating units in the polymer and has avalue of at least 10 (e.g., 10 to 100,000). The polymer chain includesat least one end group that is derived from the first monomer, i.e., anend group including a moiety of formula E-A-, in which E preferably is afluoro substituent (F), or E is a functional group obtainable bynucleophilic displacement of F from the “A” moiety, such as azido,amino, alkylamino, arylamino, alkoxy, aryloxy, alkylthio, and similargroups. In some embodiments, E is selected from fluoro, OR⁸, NHR⁸,N(R⁸)₂, azido, CN, or SR⁸, and each R⁸ independently is an organicmoiety. When A is Het (e.g., 1,3,5-triazine), each L group is attachedto a carbon atom of the heteroaromatic ring thereof.

In yet other embodiments, the polymer can be represented by the Formula(VI):(-A-R²-A-L-R³-L)a-(-A-L¹-R⁵-L¹-A-L-R³-L)b-(A-L¹-R⁵-A-L-R³-L)c-(-A-L-R³-L)d-,wherein a, b, c, and d represent the average number of the respectiverepeating units in the polymer, and any of a, b, c, and d can be 0 orgreater, so long as the sum of a, b, c, and d has a value of at least 10(e.g., 10 to 100,000 or more), and the polymer includes at least one endgroup that is derived from the first monomer, i.e., an end group offormula E-A-, E-A-L¹-R⁵-A-, E-A-L¹-R⁵-L¹-A-, E-A-R²-A-, or E-A(-R²-A)n-,in which E preferably is a fluoro substituent (F), or E is a functionalgroup obtainable by nucleophilic displacement of F from the “A” moiety,such as azido, amino, alkylamino, arylamino, alkoxy, aryloxy, alkylthio,and similar groups. In some embodiments, E is selected from fluoro, OR⁸,NHR⁸, N(R⁸)₂, azido, CN, or SR⁸, and each R⁸ independently is an organicmoiety. Each of A, L, L¹, R², R³, and R⁵ independently are defined asthey are for the other polymer and monomer embodiments described herein.

In some embodiments, at least a portion of the first monomer includes abranching monomer of the formula F—X—F in which X includes an additionalF substituent on a sulfonyl, carbonyl or heteroaryl activating group,such that the additional F substituent also reacts with a silylsubstituent on an oxygen, sulfur or nitrogen atom linking group of thesecond monomer to form the silyl fluoride, and the activating group ofthe first monomer condenses with the linking group of the second monomerto introduce at least one branch point in the polymer. Alternatively, orin addition, the second monomer can include a branching monomer in whichZ includes an additional silyl substituent attached to an oxygen, sulfuror nitrogen atom linking group, such that the additional silylsubstituent reacts with a fluoro substituent on a sulfonyl, carbonyl, orheteroaryl activating group of the first monomer to form the silylfluoride, and the linking group of the second monomer condenses with theactivating group of the first monomer to introduce at least one branchpoint into the polymer.

In any of the polymerization methods and polymers described herein, eachof the organic moieties of the monomers, e.g., R¹, R², R³, R⁴, R⁵, andR⁸ independently can be selected from the group consisting of consistingof a hydrocarbon, a heterocycle, a carbohydrate, an amino acid, apolypeptide, a peptide analog, and a combination of two or more thereof.In some embodiments, R², R³, R⁴, R⁵, and R⁸ can include one of moresubstituent, e.g., hydroxyl, halogen, nitro, —C(O)R⁶, —C(O)OR⁶,—C(O)N(R⁶)₂, —CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—,—N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶,—N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl,alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy,heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), afatty acid, a carbohydrate, an amino acid, and a polypeptide; whereineach R⁶ independently is H, alkyl, or aryl, and v is 0, 1, or 2.

The present invention also provides polymers prepared by the methodsdescribed herein. The polymers comprise a polymeric chain having aformula selected from the group consisting of:

(-A(-R²-A)n-L-R³-L)x-;  Formula (I):

(-A-R²-A-L-R³-L)y-;  Formula (II):

(-A-L¹-R⁵-L¹-A-L-R³-L)z-;  Formula (III):

(-A-L¹-R⁵-A-L-R³-L)m-;  Formula (IV):

(-A-L-R³-L)p-; and  Formula (V):

A-R²-A-L-R³-L)a-(-A-L¹-R⁵-L¹-A-L-R³-L)b-(A-L¹-R⁵-A-L-R³-L)c-(-A-L-R³-L)d-,and  Formula (VI):

at least one end group derived from the first monomer, as describedabove, i.e., including at least one functional group “E-A-” in which Epreferably is a fluoro substituent (F), or E is a functional groupobtainable by nucleophilic displacement of F from the “A” moiety, suchas azido, amino, alkylamino, arylamino, alkoxy, aryloxy, alkylthio, andsimilar groups. In some embodiments, E is selected from fluoro, OR⁸,NHR⁸, N(R⁸)₂, azido, CN, or SR⁸, and each R⁸ independently is an organicmoiety.

In the forgoing Formulas (I), (II), (III), (IV), (V), and (VI), each Aindependently is SO₂, C(═O), or Het, preferably SO₂; each R² and R⁵independently comprises a first organic moiety; each Het independentlyis an aromatic heterocycle comprising at least two carbon atoms and atleast nitrogen atom in a heteroaromatic ring thereof (preferably1,3,5-triazine); each L and L¹ independently is O, S, or N(R⁴),preferably O; each R³ and R⁵ independently comprises a second organicmoiety; each R⁴ independently is a third organic moiety; each of x, y,z, m, a, b, c, and d is the average number of respective repeating unitsin the polymer chain; each of x, y, z, m, and p has a value of at least10 (e.g., 10 to 100,000 or more); and each of and a, b, c, and d can be0 or greater, so long as the sum of a, b, c, and d has a value of atleast 10 (e.g., 10 to 100,000 or more). Each of A, L, L¹, R², R³, and R⁵independently are defined as described above for the monomer formulas.

In any of the polymers described herein each of the organic moieties,e.g., R², R³, R⁴, R⁵, and R⁸, independently can be selected from thegroup consisting of consisting of a hydrocarbon, a heterocycle, acarbohydrate, an amino acid, a polypeptide, a peptide analog, and acombination of two or more thereof. Additionally, R², R³, R⁴, R⁵, and R⁸can be substituted with one or more functional group. Non-limitingexamples of such functional groups include e.g., hydroxyl, halogen,nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂, —CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂,R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂, —N(R⁶)OR⁶,—N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂, —OC(O)OR⁶,azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl,fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy),alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, anamino acid, a polypeptide; wherein each R⁶ independently is H, alkyl, oraryl, and v is 0, 1, or 2.

In some embodiments, preferred monomers include bisphenol fluorosulfates(e.g., bisphenol A fluorosulfate, bisphenol A bisphenol AFfluorosulfate, bisphenol S fluorosulfate, and related monomers with twophenolic groups tethered together) and bisphenol silyl ethers (e.g.,bisphenol A silyl ether, bisphenol A bisphenol AF silyl ether, bisphenolS silyl ether, and related monomers with two phenolic groups tetheredtogether).

The polymers described herein typically are thermoplastic materials thatare readily moldable and thermoformable into a wide variety ofmechanical parts and structural components. The poly(bisphenol Asulfate) polymers are resistant to hydrolysis, have relatively highdielectric constant, good impact resistance, as well as tensilestrength, modulus of elasticity, and elongation similar topolycarbonates. Such polymers can be fabricated into sheets and filmsfor use in packaging materials, construction materials, and the like,and can be used in applications such as automotive and aircraftcomponents (e.g., windscreens and the like), medical prostheses, safetygoggles, and containers (e.g., cups, bottles, and the like).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates non-limiting examples of (A) fluorinated monomers,(B) silylated monomers, and (C) monomers comprising both fluoro andsilyl groups, which can be utilized in the polymerization methodsdescribed herein.

FIG. 2 schematically illustrates selected bisphenol A monomer synthesesin Panel (a), and syntheses of poly(bisphenol A sulfate) from themonomers in Panel (b).

FIG. 3 illustrates (A) preparation of nitrogen-heterocyclic carbene-typebasic catalysts from precursor materials and (B) the structures ofvarious classes of nitrogen-heterocyclic carbenes.

FIG. 4 provides normalized GPC traces of poly(bisphenol A sulfate)prepared at different monomer concentrations by polymerization ofmonomers 2a and 2b.

FIG. 5 illustrates the effect of temperature and catalyst loading on thesolution polymerization of monomers 2a+2b (lower curve) and monomers2a+2c (upper curve).

FIG. 6 provides selected GPC traces relating to the polymers in Table 2.

FIG. 7 provides Thermogravimetric Analysis (TGA) thermograms ofrepresentative poly(bisphenol A sulfate) polymer samples demonstratingconsistent thermal decomposition properties for polymers prepared underdifferent conditions and having different molecular weightcharacteristics, i.e., MALS M_(n) values of 2.5 kDa (lowest curve), 40kDa and 59 kDa (two overlapping upper curves).

FIG. 8 provides differential scanning calorimetry (DSC) second-heatingthermograms (inset) for representative poly(bisphenol A sulfate) polymersamples and a graph of corresponding GPC M_(n) versus T_(g) for thepolymers.

FIG. 9 provides tensile stress-strain curves for compression moldedpoly(bisphenol A sulfate) in comparison to commercial LEXANpolycarbonate that was compression molded in a similar manner.

FIG. 10 schematically illustrates a preparation of poly(bisphenol Acarbonate) by the polymerization methods described herein.

FIG. 11 illustrates chemical structural formulas for selected sulfonateand sulfate polymers synthesized from different monomer combinations,which demonstrate the broad scope of the polymerization methodsdescribed herein.

FIG. 12 illustrates modification of the fluorosulfate end groups of apoly(bisphenol A sulfate) prepared by the polymerization methoddescribed herein to attach a dye (Nile Red) to the ends of the polymerchains.

FIG. 13 provides UV/Visual spectra of the Nile Red dye end-cappedpoly(bisphenol A sulfate) illustrated in FIG. 12.

FIG. 14 provides graphs of refractive index versus concentration fordetermining the dn/dc of poly(bisphenol A sulfate); Panel (a) providesdata for Run #1, and Panel (b) provides data for Run #2 as described inExample 11 herein.

FIG. 15 provides (A) a GPC trace of poly(bisphenol A sulfate) preparedby the method of Firth (U.S. Pat. No. 3,733,304); and (B) a GPC trace ofpoly(bisphenol A sulfate) prepared according to the bulk polymerizationmethod described in Example 1 herein.

FIG. 16 provides GPC traces of poly(bisphenol A sulfate) from variousbatches prepared under the same target conditions at different reactionscales, as well as samples that have been heated or processed afterisolation.

FIG. 17 illustrates (A) the synthesis of sulfonylfluoride monomers fromamines by treatment with ethylene sulfonylfluoride (ESF); (b) selectedmonomers prepared according to the scheme in (A); and (C) selectedcopolymers prepared from the sulfonylfluoride monomers.

DETAILED DESCRIPTION

The present polymerization method can provide a wide variety of monomerstructures, functional substituents, and monomer-to-monomer linkages. Insome embodiments, the polymerization method comprises, consistsessentially of, or consists of contacting at least one a bis-fluorinatedfirst monomer, F—X—F, with at least one bis-silylated second monomer,(R¹)₃Si—Z—Si(R¹)₃, in the presence of a basic catalyst. The fluorosubstituents of the first monomer are attached to a sulfonyl, carbonyl,or heteroaryl portion of X, and the silyl groups of the second monomerare attached to an oxygen, sulfur or nitrogen atom of Z. In the presenceof the basic catalyst, a fluoro substituent of the first monomer reactswith a silyl substituent of the second monomer to form a silyl fluoridecompound. At the same time, a sulfonyl, carbonyl, or heteroaryl group ofthe first monomer condenses with an oxygen, sulfur or nitrogen atom ofthe second monomer to which the silyl groups was attached, to therebyform a linear alternating polymer chain with X—Z repeating units.

As described in detail herein, the first monomer can be represented bythe formula F-A(-R²-A)n-F, wherein each A independently is SO₂, C(═O),or Het; R² comprises a first organic moiety; n is 0 or 1; and Het is anaromatic heterocycle comprising at least two carbon atoms (e.g., 2 to 4)and at least one (e.g., 1 to 4) nitrogen atoms in a heteroaromatic ringthereof. When A is Het, each F is attached to a carbon atom of theheteroaromatic ring. A particularly preferred A group is SO₂. When n is0, the first monomer can be represented by the formula F-A-F (i.e.,FSO₂F, FC(O)F, and F-Het-F). When n is 1, the first monomer can berepresented by the formula F-A-R²-A-F. In some embodiments, firstorganic moiety, R², can be represented by the formula -L¹-R-L¹-, inwhich in which each L¹ independently is selected from the groupconsisting of O, S, and N(R⁴); R⁵ comprises a first organic moiety, andR⁴ is H or a third organic moiety. In some other embodiments, the firstorganic moiety, R², can be represented by the formula -L¹-R⁵—, in whichin which L¹ independently is selected from the group consisting of O, S,and N(R⁴); R⁵ comprises a first organic moiety, and R⁴ is H or a thirdorganic moiety.

The second monomer, (R¹)₃Si—Z—Si(R¹)₃, can be represented by the formula(R¹)₃Si-L-R³-L-Si(R¹)₃, in which each L independently is O, S, or N(R⁴);R³ comprises a second organic moiety; and R⁴ is H or a third organicmoiety.

FIG. 1 illustrates non-limiting examples of (A) fluorinated monomers,(B) silylated monomers, and (C) monomers comprising both fluoro andsilyl groups, which can be utilized in the polymerization methodsdescribed herein.

The X and Z portions of the polymer chain are connected to each otherthrough a linkage such as —SO₂-L-, —C(═O)-L-, -Het-L-, -L¹-SO₂-L-,-L¹-C(═O)-L-, or -L-Het-L-, in which each L and L¹ independently isselected from the group consisting of O, S, and N(R⁴); and each R⁴independently comprises H or an organic moiety. As described herein, Zcomprises an organic moiety bearing the oxygen, sulfur or nitrogenatoms, and X can be the sulfonyl, carbonyl, or heteroaryl activatinggroup, or alternatively, X can comprise an organic core group bearingthe sulfonyl, carbonyl, or heteroaryl activating groups. In some polymerembodiments, the sulfonyl, carbonyl, and heteroaryl activating groups ofX are attached directly to a carbon atom of the first organic moiety (ifpresent) in X. Alternatively, or in addition, the sulfonyl, carbonyl,and heteroaryl groups of X can be attached to the organic moiety thereofthrough a sulfur, oxygen, or nitrogen atom.

The heteroaryl groups (also referred to herein as heteroaromatic groups,or “Het”) to which the fluoro substituents of the first monomer can beattached include any heterocyclic moiety that comprises at least onenitrogen atom (e.g., 1 to 4 nitrogen atoms), and at least two carbonatoms (e.g., 2 to 4 carbon atoms) in an aromatic ring (e.g., a5-membered aromatic ring or 6-membered aromatic ring), and the fluorosubstituents are attached to carbon atoms in the aromatic ring.

Non-limiting examples of suitable heteroaryl groups, Het, comprising a6-membered heteroaromatic ring include azabenzene heterocyclic groupssuch as a pyridine, a diazine (e.g., a 1.2-diazine, a 1,3-diazine or a1,4-diazine), and a triazine (e.g., a 1,3,5-triazine); azanaphthalenegroups such as a 1-azanaphthalene (also known as a quinoline), a2-azanaphthalene (also known as an isoquinoline), a 1,2-diazanaphthalene(also known as a cinnoline), a 2,3-diazanaphthalene (also known as aphthalazine), a 1,3-diazanaphthalene (also known as a quinazoline), a1,4-diazanaphthalene (also known as a quinoxaline), a1,5-diazanaphthalene, a 1,6-diazanaphthalene, a 1,7-diazanaphthalene, a1,8-diazanaphthalene, a 1,3,5-triazanaphthaline, a1,3,8-triazanaphthalene, and a 1,3,5,8-tetraazanaphthaline (also knownas a pteridine), azaphenanthroline groups such as a1,10-diazaphenanthroline; and the like. Non-limiting examples ofsuitable heteroaryl groups, Het, comprising a 5-membered heteroaromaticring include a pyrrole, an imidazole, an oxazole, a thiazole, apyrazole, an isoxazole, an isothiazole, as well as condensed 5- and6-membered heterocycles such as an indole, an isoindole, abenzothiazole, a benzoxazole, a purine, and the like.

As described herein, the Z portion of the second monomer, andoptionally, the X portion of the first monomer can comprise any organicmoiety (e.g., R², R³, R⁴ and R⁵) groups in the formulas describedherein, since the reactivity of the monomers toward polymerizationprimarily is controlled by the basic catalyst, and the combination ofthe activating sulfonyl, carbonyl, and heteroaryl groups of the firstmonomer, the oxygen, sulfur and nitrogen atoms in the second monomer,and the formation of the thermodynamically stable silyl fluoridebyproduct from the respective fluoro and silyl substituents of the firstand second monomers.

Non-limiting examples of bis-fluorinated and bis-silylated monomers thatcan be utilized in the methods described herein, are shown in FIG. 1.Panel A of FIG. 1 illustrates selected fluorinated monomers; Panel B ofFIG. 1 illustrates selected silyl monomers; while Panel C of FIG. 1illustrates selected monomers including both fluoro and silylsubstituents.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. Allnumerical values obtained by measurement (e.g., weight, concentration,physical dimensions, removal rates, flow rates, and the like) are not tobe construed as absolutely precise numbers, and should be considered toencompass values within the known limits of the measurement techniquescommonly used in the art. All methods described herein can be performedin any suitable order unless otherwise indicated herein or otherwiseclearly contradicted by context. The use of any and all examples, orexemplary language (e.g., “such as”) provided herein, is intended merelyto better illuminate certain aspects of the invention and does not posea limitation on the scope of the invention unless otherwise claimed. Nolanguage in the specification should be construed as indicating anynon-claimed element as essential to the practice of the invention.

As used herein, the term “organic” and grammatical variations thereof,in reference to a group or moiety, refer to a material comprisingcarbon, typically in combination with at least some hydrogen, andoptionally including one or more other element, such as oxygen, sulfur,nitrogen, phosphorous, a halogen, or another non-metal or metalloidelement from groups II-A (e.g., B), IV-A (e.g., Si), V-A (e.g., As),VI-A (e.g., Se) of the periodic table. The term “organic” also refers tomaterials traditionally described as organometallic materials (e.g.,comprising one or more main group of or transition metal atomscovalently bound to a carbon atom), as well as materials that includemetallic elements in a complex or as a salt with an organic moiety.Non-limiting examples of organic moieties or groups include,hydrocarbons, heterocycles (including materials comprising at least onesaturated, unsaturated and/or aromatic ring comprising at least onecarbon atom, and one or more other elements), carbohydrates (includingsugars and polysaccharides), amino acids, polypeptides (includingproteins and other materials comprising at least two amino acid groupsbound together via a peptide bond), peptide analogs (including materialscomprising two or more amino acids linked by a bond other than a peptidebond, e.g., ester bonds), and a combination of two or more thereof.

Additionally, the organic moieties R², R³, R⁴, R⁵ and R⁸ can besubstituted with one or more functional group. Non-limiting examples ofsuch functional groups include e.g., hydroxyl, halogen, nitro, —C(O)R⁶,—C(O)OR⁶, —C(O)N(R⁶)₂, —CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—,—N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶,—N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl,alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy,heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), afatty acid, a carbohydrate, an amino acid, a polypeptide; wherein eachR⁶ independently is H, alkyl, or aryl, and v is 0, 1, or 2.

The term “hydrocarbon” and grammatical variations thereof is well knownin the art and refers to an organic compound consisting entirely ofhydrogen and carbon. Hydrocarbons can be saturated (contain no multiplebonds), unsaturated (containing at least one double or triple bond, oraromatic (containing an aromatic ring system such as a benzene ring, ora condensed aromatic ring system such as a naphthalene, anthracene, andsimilar systems). Hydrocarbons can include of linear chains of carbonsatoms, branched chains of carbon atoms, rings of carbon atoms, or anycombination thereof. Non-limiting examples of hydrocarbons includealkanes, alkenes, alkynes, cycloalkanes and alkyne-based compounds.

The term “hydrocarbyl” and grammatical variations thereof refers tounivalent groups formed by removing a hydrogen atom from a hydrocarbon,e.g. ethyl, phenyl.

The term “carbohydrate” and grammatical variations thereof is well knownin the art refers to, for example, polyhydroxylated compounds thatformally have an empirical elemental formula (CH₂O)x in which x is >1.Non-limiting examples of carbohydrates include sugars (e.g., glucose,maltose), polysaccharides (e.g., starches, cellulose), and modifiedversions of sugars and polysaccharides (e.g., comprising one or morefunctional group in place of or in addition to hydroxyl groups, such asamino, ethers, esters), as well as deoxy sugars and deoxypolysaccharides (i.e., sugars and polysaccharides in which an OH hasbeen replaced by an H), and the like. The carbohydrates can be naturallyoccurring materials, synthetic materials, or a combination thereof.

The term “amino acid” and grammatical variations thereof is well knownin the art and refers to, for example, organic compounds comprising atleast one amino group, and at least one carboxylic acid group. Examplesof amino acids include natural or synthetic alpha-amino acids (e.g., thecommon proteogenic amino acids, as well as non-proteogenic amino acidssuch as ornithine, which can be chiral materials, e.g., levo or dextrostereoisomers, or mixtures thereof, or achiral materials, depending onthe structure), as well as compounds in which the amino group andcarboxylic acid group are separated by more than one carbon.

The term “polypeptide” and grammatical variations thereof is well knownin the art and refers to, e.g., materials including two or more aminoacids (generally alpha-amino acids) joined together by peptide (amide)bonds between the carboxylic acid group (typically an alpha-carboxylicacid group) of one amino acid and the amino group (typically thealpha-amino group) of another amino acid. As used herein, the termpolypeptide also encompasses proteins, as well as materials having apolypeptide core structure with additional functional or protectinggroups appended to the polypeptide backbone. The term “peptide analog”and grammatical variations thereof refers to polypeptide-like materialsin which one or more peptide bond is replaced by a non-peptide linkage,such as an ester, an ether, and the like.

Molecular weight values such as number average molecular weight (M_(n))and weight average molecular weight (M_(w)), as well as polydispersityindex values (“PDI”, i.e., M_(w)/M_(n)) used herein are based on eithergel permeation chromatography (GPC) versus polystyrene standards, or GPCcoupled with multiangle light scattering (MALS), as described, e.g., inExample 11, below, unless otherwise specified. Molecular weightparameters for which there is no explicit description or contextualimplication of being GPC or MALS values should be interpreted asGPC-derived values. The molecular weight values are reported in units ofg/mol (also referred to as Daltons, “Da”) or Kg/mol (also referred to askDa).

Surprisingly, the polymerization methods described herein can beperformed under a variety of relatively mild reaction conditions. Thereaction routinely can be run at temperatures ranging from ambient roomtemperature (e.g., about 20 to 25° C.) to about 200° C. When thepolymerizations are performed without solvent (neat), a temperaturesufficient to melt the monomers may be desired. Preferably, the firstand second monomers are reacted in approximately equimolar amounts(based on the moles of F and silyl substituents present) or with anexcess (e.g., 0.01 up to about 10 mol % excess) of the fluorinated firstmonomer.

As described herein, the first and second monomers can be contacted withone another neat or in a solvent. Non-limiting examples of suitablesolvents include a halogenated hydrocarbons (e.g., dichloromethane,chloroform, carbon tetrachloride, perchloroethane, chlorofluorocarbons,fluorocarbons, and the like), ethers (e.g., diethyl ether,tetrahydrofuran, dimethoxyethane, and the like), esters (e.g., ethylacetate), nitriles (e.g., acetonitrile, and the like), ketones (e.g.,acetone, methylethylketone), pyridines (e.g., pyridine, picolines, andthe like), amides (e.g., N-methylpyrrolidone, acetamide,dimethylacetamide, and the like), sulfoxides (e.g., dimethylsulfoxide,and the like), and sulfones (e.g., sulfolane, dimethylsulfone, and thelike). Preferably, the solvent is non-aqueous and aprotic. If desired,mixed solvent systems can be used, or the polymerization reaction can beperformed sequentially in different solvents or in a combination ofsolventless and solution conditions (e.g., beginning in one solvent (orsolventless) and completing the polymerization in another solvent).

The silyl fluoride byproduct of the polymerization is readily separablefrom the polymer product by any of a number of methods that arewell-known to those of ordinary skill in the chemical arts. For example,the silyl fluoride can be removed by distillation or evaporation eitherat ambient atmospheric pressure or reduced pressure, depending of theboiling point of the silyl fluoride. Alternatively, or in addition,silyl fluoride byproducts, which tend to be relatively nonpolar, can beremoved from the polymer product by washing with a solvent that willdissolve the silyl fluoride but not the polymer product (e.g., ahydrocarbon solvent). The silyl fluoride byproduct also can be recycledby reaction with a salt of a bis-phenolic monomer precursor (e.g.,bisphenol A) to form a bis-silyl ether-type monomer.

The polymeric materials obtained from the methods described hereinpreferably have a degree of polymerization (i.e., average number ofmonomer units) of at least about 10 and more preferably greater than 10(e.g., 10 up to about 100, 200, 300, 400, 500, 1,000, 10,000, 100,000 orgreater).

In the methods described herein, the first and second monomers can eachcomprise a single monomeric material, or a combination to two or moremonomeric materials, either as a mixture or added sequentially to thepolymerization reactions. For example, the first monomer, F—X—F, cancomprise a combination of two or more monomeric materials with differentX groups. Similarly, the second monomer, (R¹)₃Si—Z—Si(R¹)₃, can comprisea combination of two or more monomeric materials having different R¹groups, different Z groups, or both. Such combinations of monomers canbe formulated in any desired proportion, as described herein, or can beseparately added to the polymerization mixture. The polymers resultingfrom such combinations of monomeric materials can include randomlydistributed repeating units or can include blocks of repeating monomerunits of the same structure, or both random and block segments,depending on the relative reactivity of the various monomers, as well ason whether the different monomeric materials were mixed togetherinitially, or were contacted in a serial fashion, or some combination ofmixed and serial addition.

As a non-limiting example, a mixture of first monomers can include 90mole percent (mol %) of F—SO₂—F and 10 mol % of F—SO₂—CH₂-Ph-SO₂—F.Reaction of this mixture of first monomers with a second monomer offormula Me₃Si—O-Ph-CMe₂-Ph-O—SiMe₃, would then provide a polymer ofempirical formula:—(SO₂—O-Ph-CMe₂-Ph-O-)e-(SO₂—CH₂-Ph-SO₂—O-Ph-CMe₂-Ph-O-)f-, and havingan approximate ratio of e:f of about 9:1 with the SO₂—O-Ph-CMe₂-Ph-O andSO₂—CH₂-Ph-SO₂—O-Ph-CMe₂-Ph-O repeating units likely distributed in arandom manner throughout the polymer chain. Alternatively, blockcopolymers can be formed by contacting an amount (e.g., 9 moles) of asingle first monomer composition, F—SO₂—F, and a greater molar amount(e.g., 10 moles) of single second monomer composition,Me₃Si—O-Ph-CMe₂-Ph-O—SiMe₃, to form a first uniform polymer chainsegment, —(SO₂—O-Ph-CMe₂-Ph-O-)e, and then an amount (e.g., 1 mole) of adifferent first monomer, F—SO₂—CH₂-Ph-SO₂—F, sufficient to react withthe remaining amount of the second monomer to form a second polymerchain segment (e.g., —(SO₂—CH₂-Ph-SO₂—O-Ph-CMe₂-Ph-O-)f), resulting in ablock copolymer having block segments in an approximate molar proportionof a:b (i.e., about 9:1 in this example). As will be understood by thoseof ordinary skill in the polymer art, the second monomer also oralternatively can comprise multiple compounds having different Z groups,to produce polymers having multiple combinations of repeating units, forexample, a polymer of the general formula—(X¹—Z¹)g-(X¹—Z²)h-(X²—Z¹)i-(X²—Z²)k . . . —(X′—Z′)w-, in which g, h, i,k, and w are proportional to the relative amounts of each differentfirst and second monomer present in the polymerization reaction mixture.

In some embodiments, at least a portion of the first monomer includes abranching monomer of the formula F—X—F, in which X includes anadditional F substituent on an activating group selected from SO₂,C(═O), and Het as defined elsewhere herein, such that the additional Fsubstituent also reacts with a silyl substituent of the second monomerto form a silyl fluoride, and the additional activating group condenseswith an L group of the second monomer to introduce at least one branchpoint in the polymer. For example, the first monomer can comprise orconsist of a branching monomer having an organic core group, such as aphenyl group, substituted by three activated fluoro substituents, suchas 1,3,5-tris-fluorosulfonylbenzene, or 2,4,6-trifluoro-1,3,5-triazine,in which the triazine is both the activating group (Het) and the organiccore group. Additionally, or alternatively, the second monomer caninclude a branching monomer with an additional silyl substituentattached to an oxygen, sulfur or nitrogen atom. Reaction of thebranching second monomer also results in the introduction of at leastone branch point into the polymer, by condensation of the oxygen, sulfuror nitrogen atom with a sulfonyl, carbonyl or heteroaryl activatinggroup of the first monomer, and concomitant reaction of the fluoro andsilyl substituents to form a silyl fluoride, as described herein.

In any of the polymerization method embodiments described herein, theorganic moieties, e.g., R², R³, R⁴, R⁵ and R⁸, can be selected from thegroup consisting of consisting of a hydrocarbon, a heterocycle, acarbohydrate, an amino acid, a polypeptide, a peptide analog, and acombination of two or more thereof. In some embodiments, R¹, R², R³, R⁴,and R⁵, can include one of more substituent, e.g., hydroxyl, halogen,nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂, —CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂,R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂, —N(R⁶)OR⁶,—N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂, —OC(O)OR⁶,azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl,fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy),alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, anamino acid, a polypeptide; wherein each R⁶ independently is H, alkyl, oraryl, and v is 0, 1, or 2.

An interesting and useful feature of the polymerization methodsdescribed herein is that resulting product comprises polymer chainshaving at least one and generally both ends of the chain derived fromthe first (fluorinated) monomer, such that the as-prepared polymercomprises fluoro-substituted end groups (e.g., SO₂F, COF or HetF). Thefluoro-substituted end groups can be used to functionally modify theends of the polymer chain, e.g., by nucleophilic displacement of the Fsubstituent by an oxygen, nitrogen, or sulfur-based nucleophile. Thisend group modification can be performed in the polymerization mixture atthe end of the polymerization process (e.g., when the polymerization isperformed in solution), or the resulting fluoro-capped polymer can bereacted with a nucleophile in a separate reaction after the initiallyformed polymer has been isolated. Non-limiting examples of suitablenucleophiles for displacement of the F substituent includehydroxy-substituted materials (e.g., alcohols and phenolic compounds),amines, azide, thiols, and the like.

In some embodiment, the polymers prepared by the methods describedherein comprise a polymeric chain having a formula selected from thegroup consisting of:

(-A(-R²-A)n-L-R³-L)x-;  Formula (I):

(-A-R²-A-L-R³-L)y-;  Formula (II):

(-A-L¹-R⁵-L¹-A-L-R³-L)z-;  Formula (III):

(-A-L¹-R⁵-A-L-R³-L)m-;  Formula (IV):

(-A-L-R³-L)p-; and  Formula (V):

(-A-R²-A-L-R³-L)a-(-A-L¹-R⁵-L¹-A-L-R³-L)b-(A-L¹-R⁵-A-L-R³-L)c-(-A-L-R³-L)d-.  Formula(VI):

In the forgoing Formulas (I), (II), (III), (IV), (V), and (VI), each Aindependently is SO₂, C(═O), or Het, preferably SO₂; each R² and R⁵independently comprises a first organic moiety; each Het independentlyis an aromatic heterocycle comprising at least two carbon atoms and oneto four nitrogen atoms in a heteroaromatic ring thereof, in which each Lis attached to a carbon atom of the heteroaromatic ring; each Lindependently is O, S, or N(R⁴), preferably O; each R³ independentlycomprises a second organic moiety; and each R⁴ independently is H or athird organic moiety. In Formulas (I), (II), (III), (IV), and (V) eachof x, y, z, m, and p is the average number of repeating units in thepolymer and has a value of at least 10 (e.g., 10 up to about 100, 200,300, 400, 500, 1,000, 10,000, 100,000 or more). In Formula (VI) each ofa, b, c, and d is the average number of respective repeating units andindependently can be 0 or greater, provided the sum of a, b, c, and d isat least 10 (e.g., 10 up to about 100, 200, 300, 400, 500, 1,000,10,000, 100,000 or more). The polymer chains in Formulas (I), (II),(III), (IV), and (V) includes at least one end group, an preferably twoend groups, which are derived from the first monomer, i.e., an end groupincluding the moiety E-A-, in which E preferably is a fluoro substituent(F), or E is a functional group obtainable by nucleophilic displacementof F from the “A” moiety, such as azido, amino, alkylamino, arylamino,alkoxy, aryloxy, alkylthio, and similar groups. In some embodiments, Eis selected from fluoro, OR⁸, NHR⁸, N(R⁸)₂, azido, CN, or SR⁸, and eachR⁸ independently is an organic moiety as described herein for R¹, R²,R³, R⁴, and R⁵.

An example of one class of polymers that can be produced by the methodsdescribed herein is a poly(organosulfate), such as a poly(bisphenolsulfate), as described in detail in the Examples herein. In oneembodiment, the poly(bisphenol sulfate) is represented by Formula (IV)wherein each A is SO₂, and each L is O and each R³ is a compound offormula: -Ph-C(R⁷)₂-Ph-, in which each Ph is a 1,4-phenylene group, andeach R⁷ is H, (C₁-C₄) alkyl (e.g., methyl, ethyl, and propyl), or ahalogenated (C₁-C₄) alkyl (e.g., trifluoromethyl).

In any of the polymers described herein the organic moieties, e.g., R²,R³, R⁴, R⁵, and R⁸, can be selected from the group consisting ofconsisting of a hydrocarbon, a heterocycle, a carbohydrate, an aminoacid, a polypeptide, and a combination of two or more thereof.Additionally, R², R³, R⁴, and R⁵ can be substituted with at least onefunctional group. Non-limiting examples of such functional groupsinclude e.g., hydroxyl, halogen, nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂,—CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶,—N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂,—OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl, alkenyl, alkynyl,alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl,poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, acarbohydrate, an amino acid, and a polypeptide; wherein each R⁶independently is H, alkyl, or aryl, and v is 0, 1, or 2.

In a preferred embodiment, the first and second monomers can comprise abisphenol-type compound in which two phenolic groups (capped with eithera fluorosulfonyl or silyl group) are tethered together by a linking bondor linking group (e.g., oxygen, sulfur, nitrogen, carbonyl, or asaturated or unsaturated alkylene group, which can be substituted orunsubstituted), e.g., a first monomer of Formula VII and a secondmonomer of Formula VIII:

wherein each R¹ independently is a hydrocarbyl group, and R⁹independently is a covalent bond, C(CH₃)₂, C(CF₃)₂, or SO₂.

A preferred polymer is a compound of Formula IX:

wherein t is the average number of monomer units and is at least 10(e.g., 10 up to about 100, 200, 300, 400, 500, 1,000, 10,000, 100,000 ormore), and E is F or is a functional group obtainable by nucleophilicdisplacement of F from the “A” moiety, such as azido, amino, alkylamino,arylamino, alkoxy, aryloxy, alkylthio, and similar groups. In someembodiments, E is selected from fluoro, OR⁸, NHR⁸, N(R⁸)₂, azido, CN, orSR⁸, and each R⁸ independently is an organic moiety as described hereinfor R¹, R², R³, R⁴, and R⁵.

Certain non-limiting embodiments of the methods and materials describedherein are illustrated below.

Embodiment A is a polymerization method comprising the step ofcontacting a liquid monomer composition with a basic catalyst, whereinthe monomer composition comprises at least one compound of formula F—X—Fand at least one compound of formula (R¹)₃Si—Z—Si(R¹)₃; wherein: each R¹independently is a hydrocarbyl group; X has the formula -A(-R²-A)n-;each A independently is SO₂, C(═O), or Het; R² comprises a first organicmoiety; n is 0 or 1; Het is an aromatic heterocycle comprising at leasttwo carbon atoms and at least one nitrogen atom in a heteroaromatic ringthereof, and when A is Het, the F substituent is attached to a carbonatom of the heteroaromatic ring thereof; Z has the formula -L-R³-L-;each L independently is O, S, or N(R⁴); R³ comprises a second organicmoiety; each R⁴ independently is H or a third organic moiety; andwherein the F and (R¹)₃Si substituents form a silyl fluoride byproductof formula (R¹)₃Si—F as the respective A and L groups of the monomerscondense to form an X—Z polymer chain; and wherein the basic catalystcomprises at least one material selected from the group consisting of anamidine, a guanidine, a phosphazene, a nitrogen heterocyclic carbene, atertiary alkoxide, and a fluoride salt.

Embodiment B is the method of Embodiment A wherein: each R¹independently is an alkyl or aryl group; X has the formula -A(-R²-A)n-;each A is SO₂; R² comprises a first organic moiety; n is 0 or 1; Z hasthe formula -L-R³-L-; each L independently is O; and R³ comprises asecond organic moiety comprising at least one aryl or heteroaryl groupdirectly bonded to each L.

Embodiment C is the method of Embodiment A or B wherein the n is 0.

Embodiment D is the method of any one of Embodiments A to C wherein Hetis a 1,3,5-triazine.

Embodiment E is the method of any one of Embodiments A to D wherein themonomer composition includes a compound in which X includes anadditional F substituent on a sulfonyl, carbonyl, or heteroarylactivating group, A, such that the additional F substituent also reactswith a (R¹)₃Si substituent on an oxygen, sulfur or nitrogen atom linkinggroup, L, to form a silyl fluoride, and the activating group condenseswith the linking group to introduce a branch point in the polymer.

Embodiment F is the method of any one of Embodiments A to E wherein themonomer composition includes a compound in which Z includes anadditional silyl substituent, (R¹)₃Si, on an oxygen, sulfur or nitrogenatom linking group, L, such that the additional silyl substituent alsoreacts with a F substituent on a sulfonyl, carbonyl, or heteroarylactivating group, A, to form a silyl fluoride and the linking groupcondenses with the activating group to introduce a branch point in thepolymer.

Embodiment G is the method of any one of Embodiments A to F wherein n is1; R² is -L¹-R-L¹-; each L¹ independently is selected from the groupconsisting of O, S, and N(R⁴); and each R⁴ independently is H or thethird organic moiety, and R⁵ comprises an organic moiety.

Embodiment H is the method of any one of Embodiments A to G wherein n is1; R² is -L¹-R⁵—; L¹ is selected from the group consisting of O, S, andN(R⁴); R⁴ s H or the third organic moiety; and R⁵ is an organic moiety.

Embodiment I is the method of any one of Embodiments A to H wherein thebasic catalyst comprises 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

Embodiment J is the method of any one of Embodiments A to I wherein thebasic catalyst comprises at least one phosphazene selected from thegroup consisting of2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine(BEMP) and1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ⁵,4λ⁵-catenadi(phosphazene)(P₄-t-Bu).

Embodiment K is the method of any one of Embodiments A to J wherein thebasic catalyst comprises at least one fluoride salt selected from thegroup consisting of CsF, CsFHF, KF, tetrabutylammonium fluoride (TBAF)and tris(dimethylamino)sulfonium-difluorotrimethylsilicate (TASF).

Embodiment L is the method of any one of Embodiments A to K wherein thebasic catalyst comprises at least one guanidine selected from the groupconsisting of 1,1,3,3-tetramethylguanidine (TMG),1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene (MTBD).

Embodiment M is the method of any one of Embodiments A to L wherein thebasic catalyst comprises at least one nitrogen-heterocyclic carbeneselected from the group consisting of an imidazole-2-ylidene, a1,2,4-triazole-5-ylidene, a thiazole-2-ylidene, and animidazolin-2-ylidene.

Embodiment N is the method of any one of Embodiments A to M wherein eachA is SO₂.

Embodiment O is the method of any one of Embodiments A to N wherein eachR² comprises an aryl or heteroaryl moiety either directly bonded to an Agroup or bonded to A via an oxygen atom attached to the aryl orheteroaryl moiety.

Embodiment P is the method of any one of Embodiments A to O wherein thepolymer comprises a polymeric chain represented by a formula selectedfrom the group consisting of:

(-A(-R²-A)n-L-R³-L)x-;  Formula (I):

(-A-R²-A-L-R³-L)y-;  Formula (II):

(-A-L¹-R⁵-L¹-A-L-R³-L)z-;  Formula (III):

(-A-L¹-R₅-A-L-R³-L)m-;  Formula (IV):

(-A-L-R³-L)p-; and  Formula (V):

(-A-R²-A-L-R³-L)a-(-A-L¹-R⁵-L¹-A-L-R³-L)b-(A-L¹-R⁵-A-L-R³-L)c-(-A-L-R³-L)d-;  Formula(VI):

wherein: each A independently is SO₂, C(═O), or Het; each L and L¹independently is O, S, or N(R⁴); each R² and R⁵ independently comprisesa first organic moiety; each R³ comprises a second organic moiety; eachR⁴ independently is H or a third organic moiety; each n independently is0 or 1; each Het independently is an aromatic heterocycle comprising atleast two carbon atoms and at least one nitrogen atom in aheteroaromatic ring thereof, and when A is Het, the F substituent isattached to a carbon atom of the heteroaromatic ring thereof; each of x,y, z, m, and p is the average number of repeating units in the polymerand has a value of at least 10; and each of a, b, c, and d is theaverage number of respective repeating units, and independently can be 0or greater, provided the sum of a, b, c, and d is at least 10.

Embodiment Q is the method of any one of Embodiments A to P wherein oneor more of the R², R³, R⁴, and R⁵, comprises a moiety selected from thegroup consisting of a hydrocarbon, a heterocycle, a carbohydrate, anamino acid, a polypeptide, a peptide analog, and a combination of two ormore thereof.

Embodiment R is the method of any one of Embodiments A to Q wherein oneor more of R¹, R², R³, R⁴, and R⁵ is substituted by at least onesubstituent selected from the group consisting of hydroxyl, halogen,nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂, —CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂,R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂, —N(R⁶)OR⁶,—N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂, —OC(O)OR⁶,azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl,fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy),alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, anamino acid, and a polypeptide; wherein each R⁶ independently is H,alkyl, or aryl, and v is 0, 1, or 2.

Embodiment S is the method of any one of Embodiments A to R wherein themonomer composition comprises (a) two or more different compounds offormula F—X—F, (b) two or more different compounds of formula(R¹)₃Si—Z—Si(R¹)₃, or (c) c combination of both (a) and (b).

Embodiment T is the method of Embodiment S wherein the two or moredifferent compounds of formula (R¹)₃Si—Z—Si(R¹)₃ differ by the selectionof R¹, Z, or both R¹ and Z.

Embodiment U is the method of any one of Embodiments A to T wherein themonomer composition comprises at least one compound of Formula VII andat least one compound of Formula VIII:

wherein each R¹ independently is an alkyl or aryl group, and each R⁹independently is a covalent bond, C(CH₃)₂, C(CF₃)₂, or SO₂.

Embodiment V is the method of any one of Embodiments A to U wherein theliquid monomer mixture comprises a mixture of the monomers dissolved ina solvent.

Embodiment W is the method of any one of Embodiments A to V wherein theliquid monomer mixture comprises a melted mixture of the monomers.

Embodiment X is the method of any one of Embodiments A to W wherein theF—X—F monomer comprises sulfuryl fluoride (FSO₂F).

Embodiment Y is the method of any one of Embodiments A to W wherein theF—X—F monomer comprises a bisfluorosulfonyl monomer of formulaF—SO₂—CH₂CH₂—N(R¹¹)—CH₂CH₂—SO₂—F, wherein R¹¹ comprises an organicmoiety.

Embodiment Z is the method of Embodiment Y wherein R¹¹ comprises amoiety selected from the group consisting of a hydrocarbon, aheterocycle, a carbohydrate, an amino acid, a polypeptide, a peptideanalog, and a combination of two or more thereof.

Embodiment AA is the method of Embodiment Y or Embodiment Z wherein R¹¹is substituted by at least one substituent selected from the groupconsisting of hydroxyl, halogen, nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂,—CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶,—N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂,—OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl, alkenyl, alkynyl,alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl,poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, acarbohydrate, an amino acid, and a polypeptide; wherein each R⁶independently is H, alkyl, or aryl, and v is 0, 1, or 2.

Embodiment AB is a polymer comprising a polymeric chain having a formulaselected from the group consisting of:

(-A(-R²-A)n-L-R³-L)x-;  Formula (I):

(-A-R²-A-L-R³-L)y-;  Formula (II):

(-A-L¹-R⁵-L¹-A-L-R³-L)z-;  Formula (III):

(-A-L¹-R⁵-A-L-R³-L)m-;  Formula (IV):

(-A-L-R³-L)p-; and  Formula (V):

(-A-R²-A-L-R³-L)a-(-A-L¹-R⁵-L¹-A-L-R³-L)b-(A-L¹-R⁵-A-L-R³-L)c-(-A-L-R³-L)d-;  Formula(VI):

wherein: each A independently is SO₂, C(═O), or Het; each L and L¹independently is O, S, or N(R⁴); each R² and R⁵ independently comprisesa first organic moiety; each R³ comprises a second organic moiety; eachR⁴ independently is H or a third organic moiety; each n independently is0 or 1; each Het independently is an aromatic heterocycle comprising atleast two carbon atoms and at least one nitrogen atom in aheteroaromatic ring thereof, and when A is Het, the F substituent isattached to a carbon atom of the heteroaromatic ring thereof; each of x,y, z, m, and p is the average number of repeating units in the polymerand has a value of at least 10; and each of a, b, c, and d is theaverage number of respective repeating units, and independently can be 0or greater, provided the sum of a, b, c, and d is at least 10; and thepolymer includes a group of formula E-A- at one or both ends of thepolymer chain, wherein each E independently is fluoro, OR⁸, NHR⁸,N(R⁸)₂, azido, CN, or SR⁸, and each R⁸ independently is an organicmoiety.

Embodiment AC is the polymer of Embodiment AB wherein one or more of theorganic moieties R², R³, R⁴, R⁵ and R⁸ is selected from the groupconsisting of a hydrocarbon, a heterocycle, a carbohydrate, an aminoacid, a polypeptide, a peptide analog, and a combination of two or morethereof.

Embodiment AD is the polymer of Embodiment AB or AC wherein one or moreof R², R³, R⁴, R⁵ and R⁸ is substituted by at least one substituentselected from the group consisting of hydroxyl, halogen, nitro, —C(O)R⁶,—C(O)OR⁶, —C(O)N(R⁶)₂, —CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—,—N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶,—N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl,alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy,heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), afatty acid, a carbohydrate, an amino acid, and a polypeptide; whereineach R⁶ independently is H, alkyl, or aryl, and v is 0, 1, or 2.

Embodiment AE is the polymer of Embodiment AB wherein the polymercomprises a compound of Formula IX:

wherein t is the average number of monomer units and is at least 10,each E independently is fluoro, OR⁸, NHR⁸, N(R⁸)₂, azido, CN, or SR⁸,and each R⁸ independently is an organic moiety.

Embodiment AF is the polymer of any one of Embodiments AB to AD whereinthe polymer has the Formula (I): (-A(-R²-A)n-L-R³-L)x-, in which each Ais SO₂, and each R² independently is —CH₂CH₂—N(R¹¹)—CH₂CH₂—, wherein R¹¹comprises an organic moiety.

Embodiment AG is the polymer of Embodiment AF wherein R¹¹ comprises amoiety selected from the group consisting of a hydrocarbon, aheterocycle, a carbohydrate, an amino acid, a polypeptide, a peptideanalog, and a combination of two or more thereof.

Embodiment AH is the polymer of Embodiment AF or AG wherein R¹¹ issubstituted by at least one substituent selected from the groupconsisting of hydroxyl, halogen, nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂,—CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶,—N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂,—OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl, alkenyl, alkynyl,alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl,poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, acarbohydrate, an amino acid, and a polypeptide; wherein each R⁶independently is H, alkyl, or aryl, and v is 0, 1, or 2.

Embodiment AI is the polymer of Embodiment AB wherein the polymer has amolecular weight polydispersity index (PDI) of less than about 2.2 basedon gel permeation chromatography using polystyrene standards, andincluding less than about 5 percent by weight of cyclic oligomers.

Embodiment AJ is the polymer of Embodiment AI wherein the polymer ispoly(bisphenol A sulfate).

Embodiment AK is a transparent, substantially colorless film or sheetcomprising poly(bisphenol A sulfate).

Embodiment AL is a method of preparing the film or sheet of EmbodimentAK comprising pelletizing poly(bisphenol A sulfate), and compressing thepellets at an elevated pressure at a temperature greater than the glasstransition temperature thereof.

Embodiment AM is the method of Embodiment AL wherein the elevatedpressure is at least about 25,000 pounds-per-square inch (psi) and thetemperature is in the range of about 200 to 250° C.

In any of the embodiments described herein, one or more of the A groups(i.e., SO₂, C(═O), or Het) of the fluorinated monomer, F—X—F, can bereplaced with a group of formula S(═O)(═NR¹²), i.e., to form a monomerwith a —S(═O)(═NR¹²)F functional group in place of an SO₂F, C(═O)F, orHet-F group.

Certain aspects and features of the methods and polymers describedherein are further illustrated in the following, non-limiting examples.

Example 1 Exemplary Poly(Bisphenol A Sulfate) Preparations Large scalepreparation of propane-2,2-diylbis(4,1-phenylene)difluorosulfonate (2a)

A 2-liter single-neck round-bottom flask was charged with bisphenol A(114.9 g, 0.5 mol), CH₂Cl₂ (DCM; 1 L) and triethylamine (Et₃N; 174 mL,1.25 mol, 2.5 equivalents). The mixture was stirred at room temperaturefor 10 minutes (min). The reaction flask was then sealed with a septum,the atmosphere above the solution was removed with gentle vacuum, andSO₂F₂ gas (sulfuryl fluoride, VIKANE) was introduced by needle from aballoon filled with the gas. For large scale reactions such as this,depletion of the sulfuryl fluoride from the balloon was easily observed,and more reagent was introduced with a fresh balloon when required. Forsmall scale reactions, SO₂F₂ was used in excess. These reactions can beeasily followed by thin layer chromatography (TLC).

The reaction mixture was vigorously stirred at room temperature for 2-4hours, monitoring by GC-MS and TLC. After completion, the solvent wasremoved by rotary evaporation, the residue was dissolved in ethylacetate (EtOAc; 1 L), and the solution was washed with 1N HCl (2×500 mL)and brine (2×500 mL). The organic phase was dried over anhydrous Na₂SO₄and concentrated. The resulting solid was dried under high vacuum at 60°C. overnight to give the desired compound as a white crystalline solidin quantitative yield (197.1 g, 100% yield). Melting point (mp) 48-49°C. ¹H NMR (400 MHz, CDCl₃) δ 7.34-7.32 (m, 2H), 7.28-7.26 (m, 2H), 1.72(s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 150.4, 148.2, 128.7, 120.5, 42.9,28.4, 30.7; ¹⁹F NMR (376 MHz, CDCl₃) δ+37.0; GC-MS (t_(R)): 7.2 min;EI-MS (m/z): 392 [M]⁺.

Large scale preparation of(propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(tert-butyldimethylsilane(2c)

In a 2 L flask, 88.4 grams (2.6 eq., 1.3 mol) of imidazole was adding toa solution of bisphenol A (114.2 gram, 0.5 mol) in DCM (1000 mL), thissolution stirred at room temperature for 10 min. Next, 181 gram oft-butyldimethylsilyl chloride (TBSCl; 2.4 equivalents, 1.2 mol) wasdissolved into 200 mL of DCM, and the resulting TBSCl solution was addedto the bisphenol A over 30 minutes by addition funnel. the reaction wasstirred at room temperature for 24 hours. And the reaction was monitoredby TLC or GCMS. Then the DCM solvent and was removed by rotaryevaporation, 1000 mL of EtOAc was added to re-dissolve the residue, theEtOAc solution was washed twice with 500 mL saturated sodium bicarbonatesolution, twice with 500 mL brine, and then the organic phase was driedover anhydrous Na₂SO₄. Removed the solvents by rotary evaporation. Theresulting product was dried under high vacuum at 70 OC for 24 hours. Thepure bis-TBS bisphenol A compound was obtained as a white solid (225.2grams, 98.5% yield) without need for further purification beforepolymerization reaction. mp 78-80° C.; ¹HNMR: (400 MHz, CDCl₃, 23° C.):δ 7.10-7.07 (m, 4H), 6.76-6.73 (m, 4H), 1.65 (s, 6H), 1.01 (s, 18H),0.22 (s, 12H). ¹³CNMR: (100 MHz, CDCl₃, 23° C.): δ 153.2, 143.7, 127.7,119.2, 41.7, 31.1, 25.7, 18.2, −4.39. GCMS: 8.38 min, MS m/z 456.3 (M+).

Large Scale Bulk Polymerization—(0.5 Mol Scale) of Poly(Bisphenol ASulfate).

A 1,000 mL 3-necked round bottom flask equipped with a reflux condenser,two rubber septa (one of which contained a thermometer for internalmeasurements) and a Teflon-coated magnetic stir bar was charged with 2a(98.1 g, 0.25 mol) and 2c (114.5 g, 0.25 mol). The reaction vessel wasplaced into an oil bath and brought to 135° C. Once the monomers melted(internal temperature 120° C.), 1 mol % of BEMP as a 1M solution inhexanes (5 mL, 5 mmol) was added. Within 5 min,tert-butyldimethylfluorosilane (TBSF) was observed refluxing. Afterapproximately 45 min, the reaction mixture solidified and stirringceased. Heating at 120 OC was continued for an additional 45 min atwhich point the reflux condenser was replaced by a distillation head,and TBSF was distilled off (56 g isolated). DMF (300 mL) was then addedto the solid crude BPA-polysulfate product, and heating was continued at130° C. until stirring was restored and all the polymer had dissolved.The resulting clear, colorless DMF solution was allowed to cool toapproximately 60° C. and was then slowly poured at a continuous andconsistent rate into a beaker containing 3 L of vigorously stirred(overhead stirrer) methanol at ambient temperature, resulting in theformation of long, fibrous BPA-polysulfate strands. This material (144g, 99.3%) was dried overnight at 80° C. in a vacuum oven, analyzed byGPC. PDI=1.7; M_(n)=120,000 Da referenced to polystyrene standards;M_(n)=58,000 determined by MALS; T_(g)=98° C.; ¹H NMR (400 MHz, DMSO-d₆)δ 7.31 (app s, 8H), 1.61 (2, 6H); Calcd. For (C₁₅H₁₄O₄S)_(n): C, 62.05;H, 4.86; S, 11.04. Found: C, 61.98; H, 4.80; S, 10.84; F, 0.33.

The polymerization reactions described herein are extremely efficient,and when bis(arylfluorosulfate) 2a and bis(arylsilyl) ethers 2b-e areused, high molecular weight polymers are produced (FIG. 2). The reactionis catalyzed by organic bases, such as1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaza-phosphorine(BEMP), or fluoride salts, such as CsF. It proceeds in essentiallyquantitative yields, is compatible with many functional groups, and doesnot require special equipment or precautions.

Both the fluorosulfate and the silyl ether monomers were readilyobtained from BPA (FIG. 2, Panel (a)). Its treatment with SO₂F₂ gas inthe presence of triethylamine generated the bis(fluorosulfate) 2a, whichwas isolated as a shelf-stable, white crystalline solid in high yield onmole scale following simple work-up procedures without the need forchromatographic purification. The bis(silyl ether) monomers, 2b-e areeither commercially available (2b) or were easily prepared on a largescale following standard procedures (2c-e).

The initial examination of the reaction between monomers 2a and 2b indifferent solvents (1M in monomers) in the presence of 20 mol % of DBUidentified N-methylpyrrolidone (NMP) and dimethylformamide (DMF) asoptimal solvents for the preparation of polysulfates (FIG. 2, Panel(b)). Following precipitation from methanol, BPA-polysulfate (BPA-PS)was recovered as white powder in 95% yield (GPC M_(n)=30,900 g/mol,referenced to polystyrene standards). The results were similar when theTBS monomer (2c) was used (GPC M_(n)=24,600 g/mol); in the latter case,liquid tert-butylfluorodimethylsilane (3c, TBSF) byproduct was generatedand removed by distillation.

Example 2 Catalyst Evaluation

A variety of organic and inorganic bases, nucleophiles, Lewis acids, andfluoride sources were evaluated using monofunctional fluorosulfate(PhOSO₂F) and TBS-protected phenol (PhOTBS) in acetonitrile. The resultsrevealed that amidines, guanidines and phosphazenes are particularlyuseful catalysts. Additional active catalysts were fluoride, introducedthrough organic and inorganic sources, as well as non-nucleophilictert-butoxide base (KOt-Bu).

Active catalysts were then applied to the polymerization ofBPA-fluorosulfate monomer (2a) and both TMS (2b) and TBS (2c) protectedBPA monomers at room temperature (see Table 1). The TMS monomer system,(2a+2b), offered BPA-polysulfate up to and around M_(n) 30,000 to 35,000g/mol (based on GPC), while the TBS monomer system (2a+2c) displayed awider range of obtained M_(n) values. Of the amidine catalyst, Entries1-3 in Table 1, DBU was the most effective for generating polymer, asDBN and PMDBD provided mostly oligomers. Guanidines, Entries 4-6, werelargely comparable if not superior to amidine catalysts in that MTBDgave BPA-polysulfate of twice the M_(n) with half the catalyst loading,as compared to DBU (2a+2c system). Phosphazenes, Entries 7-8, displayedthe greatest catalytic activity, as evidenced by polysulfate of 55,400g/mol produced by BEMP. Finally, catalytic KOt-Bu (Entry 9) and fluoride(Entries 10-11) gave polysulfate only with the TBS system, whereas withTMS system yielded low molecular weight (MW) oligomers. From these andother initial studies it was apparent that 2c, with the more stable TBSprotecting groups on the phenolic hydroxy substituents, offered thepotential to prepare polysulfates of higher M_(n) as compared to 2b, TMSsystem, which showed an apparent M_(n) ceiling of about 35,000 g/mol.The difference between these two systems may be related to the muchgreater basic stability of TBS phenols as compared to TMS phenols.

TABLE 1 BPA-Polysulfate Catalyst Evaluation. 2a + 2b (TMS) 2a + 2c (TBS)Entry Catalyst M_(n) PDI M_(n) PDI 1 DBU

 0,900^([a,c,e]) 1.6 24,000^([a,c,f]) 1.4 2 DBN oligomer^([a,c,e])oligomer^([a,c,f]) 3 PMDBD oligomer^([a,c,f]) no precipitate^([a,c,f]) 4TMG 30,300^([a,c,e]) 1.7 oligomer^([a,c,f]) 5 TBD 22,800^([a,d,e]) 1.5oligomer^([b,c,f]) 6 MTBD 29,600^([a,d,e]) 1.5 44,300^([b,c,f]) 1.5 7BEMP 33,900^([a,d,e]) 1.5 55,400^([b,c,f]) 1.5 8 P₄-t-Bu N/A45,100^([b,c,f]) 1.6 9 KOt-Bu oligomer^([a,d,e]) 29,700^([a,c,e]) 1.4 10CsF oligomer^([a,d,e]) 28,200^([a,c,e]) 1.4 11 TASF oligomer^([a,d,e])48,100^([a,c,f]) 1.7

In Table 1, polymerization conditions were: catalyst loading [a]20 mol %or [b]10 mol %; molarity NMP [c] about 1M or [d] about 0.5M; reactiontime [e]24 hours or [f]48 hours. Material isolated from methanolprecipitation and analyzed by GPC. M_(n) in reference to polystyrenestandards. Abbreviations: DBU=1,8-diazabicyclo[5.4.0]undec-7-ene;DBN=1,5-diazabicyclo[4.3.0]-non-5-ene;PMDBD=1,2,3,4,4a,5,6,7-octahydro-2,2,4a,7,7-pentamethylnaphthyridine;TMG=1,1,3,3-tetramethylguanidine;TBD=1,5,7-triazabicyclo[4.4.0]dec-5-ene;MTBD=7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene;BEMP=2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine;P₄-t-Bu=1-tert-butyl-4,4,4-tris-(dimerthylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ⁵,4λ⁵-catenadi(phosphazene);KOt-Bu, potassium tert-butoxide; CsF=cesium fluoride;TASF=tris(dimethylamino)sulfonium-difluorotrimethylsilicate.

Nitrogen-heterocyclic carbenes also can be used as catalysts in thepolymerization methods described herein. FIG. 3 illustrates thepreparation of nitrogen-heterocyclic carbenes from salt and zwitterionintermediates (Panel A), as well as some heterocyclic carbene classes(Panel B, which illustrates an imidazole-2-ylidene, a1,2,4-triazole-5-ylidene, a thiazole-2-ylidene, and animidazolin-2-ylidene). A representative carbene is1,3-(di-(2,4,6-trimethylphenyl)-2,3-dihydro-1H-imidazol-2-ylidene. Thesecarbene bases and their preparation are described in detail by Enders etal., Chem. Rev. 2007, 107:5606-5655, which is incorporated by referenceherein in its entirety. The reaction of monomers 2a and 2c with thezwitterionic carboxylate precursor of1,3-(di-(2,4,6-trimethylphenyl)-2,3-dihydro-1H-imidazol-2-ylidene (seeFIG. 3) releases CO₂ upon heating and produces the active catalyst insitu. On a 2 mmol scale, the GPC M_(n) of the resulting polymer was56,000 Da (polystyrene standards), and the PDI was 1.4.

The mechanism of the catalysis is not yet understood. Preliminaryinvestigations suggest that activation of silyl ethers with F⁻/HF₂ ⁻ andtheir conversion to hypervalent silicon derivatives, may possibly be atleast partially responsible for the observed reactivity of the silylethers with fluorosulfates. Interactions of DBU and similar catalystswith the fluorosulfonyl group may also or alternatively play a role inthe reaction.

Example 3 Evaluation of Concentration, Temperature and Catalyst Loading

The effect of concentration was explored with the TMS system (2a+2b).Molecular weight was highest in bulk (at about 150° C., well above theT_(g) of about 90 to 98° C.) and decreased as concentration decreased(see FIG. 4). Bulk polymerization also exhibited the lowest amount ofwhat is believed to be a cyclic oligomer byproduct, shown eluting atapproximately 23 minutes in the GPC. The narrow PDI and low M_(n), asdetermined by GPC, indicate a cyclic topology for this byproduct. Thecyclic oligomer was less soluble in organic solvents than the polymer.While the exact structure is not yet identified, the cyclic displays asymmetrical NMR and elemental analysis indicates a molecular formula of(C₁₅H₁₄O₄S)_(n) (62.32% C, 1.89% H, 11.03% S). The amount of cyclicbyproduct increased as concentration decreased. This increase in cyclicbyproduct formation is expected due to the increased tendency towardsintramolecular reaction at low concentration. A similar effect has beenobserved for BPA-polycarbonate. At low concentrations, accomplished bydrop-wise addition of 2a and 2b to a dilute acetonitrile solutioncontaining DBU, the product is almost purely cyclic oligomer. Othercatalysts screen for activity under the bulk polymerization conditionsdescribed above included BEMP, CsF and potassium tert-butoxide.Similarly to the results described above, both BEMP and CsF providedgreater M_(n) than did DBU. Interestingly, potassium tert-butoxide wasineffective, despite showing activity in solution.

The effect of temperature on the solution-based polymerization in NMPwas subsequently explored. Catalyst loading was held constant at 20%DBU. The TMS systems did not respond to heating as shown in FIG. 5(lower curve), the GPC M_(n) was roughly 35,000 g/mol. Bulkpolymerization of this TMS system was anticipated to increase M_(n) anddid so but only slightly, about 40,000 g/mol. In contrast the TBS system(FIG. 5, upper curve) demonstrated a significant increase in M_(n) whenreaction temperature was increased from room temperature to 50° C.Further increases in temperature yielded slight increases in M_(n): atthese increased temperatures, M_(n) was roughly 50,000 g/mol. At 150°C., the highest temperature explored, the M_(n) decreased, likely due todegradation.

The effect of varying catalyst loading also was examined. At roomtemperature in NMP, the TMS system (2a+2b) exhibited essentially nochange in GPC M_(n) regardless of mol % DBU employed. In the TBS system,increasing DBU loading resulted in increased M_(n). Like the firstincrease in temperature from room temperature (RT) to 50° C., the firstincrease in DBU loading from 20 to 50% gave a large jump in M_(n). MoreDBU did increase the M_(n) further but in a less pronounced manner withM_(n) reaching around 50,000 to 55,000 g/mol. In bulk at 150° C.,catalyst loading had no clear effect on M_(n), which hovered around anapparent average of 65,000 to 70,000 g/mol.

The TBS system was more responsive to different conditions than the TMSsystem, which showed clear limitation in increasing GPC M_(n). In bulk,the TBS system generated polymers of the highest molecular weight. Bulkpolymerization also affords the least cyclic byproduct and is arguably aless wasteful and more eco-friendly process. For these reasons, thescope of bulk polymerization conditions was extended further.

Further investigations showed that molecular weight of the polymersdepended on the nature of the catalyst, its loading, and the nature ofthe silyl group (Table 2, FIG. 6). The TBS monomer 2c consistentlyproduced the largest polymers, with GPC M, surpassing 100,000 g/mol whenBEMP catalyst was used, (Table 2, entry 4-6). DBU generally resulted inless than 70,000 g/mol polymers and was ineffective at low loadings (cf.entries 4 and 7). Polymers obtained from the TMS monomer 2b, in contrastto TBS, never exceeded 40,000 g/mol regardless of polymerizationconditions. TBDPS (2d) and TIPS (2e) BPA ethers also successfullypolymerized in the bulk and produced polysulfates of variable M,(entries 11 and 13), although higher loadings of the BEMP catalyst wererequired (cf. entries 10 vs. 11). Thus, the TBS ether 2c has emerged asthe “goldilocks” monomer, yielding large polymers with low catalystloadings at different conditions. Finally, several samples weresubjected to multiangle light scattering (MALS) analysis for absolutemolecular weight determination. As has been reported forBPA-polycarbonates, polystyrene standards appear to significantlyoverestimate molecular weights of polysulfates. This was especiallynoticeable for the lower molecular weight polymers (Entries 1-3 in Table2), with the error being reduced to approximately twofold for the highermolecular weight (cf. Entries 4 and 9). FIG. 6 provides representativeGPC traces for the polymers labeled A, B, C and D in Table 2 (Entries 1,3, 8, and 4, respectively).

TABLE 2 Comparison of bulk polymerization conditions. Entry MonomersCat. Mol % M_(n) ^(MALS) M_(n) ^(PS) PDI 1(A) 2a + BEMP  1% 2,500 17,0001.3 2b(TMS) 2 10% 8,800 34,000 1.4 3(B) DBU 20% 10,600 38,000 1.4 4(D)2a + BEMP  1% 58,000 120,000 1.7 2c(TBS) 5 10% n/d 128,000 1.6 6 20% n/d143,000 1.5 7 DBU  1% no polymer formation 8(C) 20% 19,600 66,000 1.4 9CsF 20% 38,300 93,000 1.5 10 2a + BEMP  1% no polymer 2d(TBDPS)formation 11 10% n/d 118,000 1.5 12 2a + BEMP  1% no polymer 2e(TIPS)formation 13 10% n/a 51,400 2.0 Notes for Table 2: Polymerizationconditions: solvent-free, 150° C., 2 hours (h). Workup: dissolution inDMF followed by subsequent precipitation from methanol. M_(n) ^(MALS)refers to M_(n) determined by multiangle light scattering coupled withGPC. M_(n) ^(PS) refers to M_(n) determined by GPC in reference topolystyrene standards. n/d = not determined.

Example 4 Poly(Bisphenol A Sulfate) Physical Property Characterization

The physical properties of the poly(bisphenol A sulfate) polymersobtained in the present examples were evaluated. Thermogravimetricanalysis (TGA) measurements were made on polymers with MALS M, of about2,500, 40,000 and 58,000 g/mol.

In particular, thermal decomposition of BPA-polysulfate samples weremeasured using a TA Q5000IR TGA with a heating rate of 10° C./min. Theglass transition temperature (T_(g)) of various polymer samples wasdetermined using a TA Q2000 differential scanning calorimetry (DSC)apparatus. A heat/cool/heat program ranging from 0° C. to 220° C. at 10°C./min was used. T_(g) was taken from the second heating scan.

The TGA results indicated that the polysulfates exhibited excellentthermal stability, with very similar degradation curves, as shown inFIG. 7, in which the curve for the 2,500 g/mol sample is the lowestcurve, and the 40,000 and 58,000 g/mol samples are shown in the upper,overlapping curves. The thermal decomposition temperature increased onlyslightly as M_(n) increased, but each material was thermally robust:only about 5% weight loss occurred at nearly 350° C.

Representative DSC thermograms of several separately poly(bisphenol Asulfate) samples are provided in FIG. 8 (inset), in which polymershaving respective MALS M_(n) values of 2.5 kDa, 10.6 kDa, 20 kDa, 38kDa, and 58 kDa were evaluated, proceeding from the top curve to thebottom curve. The T_(g) values were in the range of about 72 to 98° C.for the polymers, with the lowest M polymer having the lowest T_(g), andthe highest M polymer having the highest T_(g). No crystalline meltingor crystallization peaks were identified, indicating that the BPApolysulfate is amorphous. The aromatic sulfate backbone was also foundto be hydrolytically stable. FIG. 8 also provides a graph of M versusT_(g). The data in FIG. 8 demonstrates a plateau in the T_(g) values ofabout 95 to about 100° C. as the MALS M exceeded about 20 kDa (a GPCM_(n) of about 60 kDa). This indicates that a MALS M of about 20 kDa (orGPC M_(n) of about 60 kDa) for the poly(bisphenol A sulfate) polymersrepresents the approximate minimum molecular size to produce a fullyentangled polymer. No crystalline melting or crystallization peaks wereidentified, indicating that the tested poly(bisphenol A sulfate)polymers are amorphous.

The 120,000 g/mol M_(n) sample (based on GPC versus polystyrenestandards) also initially was analyzed by GPC coupled with multianglelight scattering (MALS) and differential refractive index (dRI)detectors for absolute molecular weight determination using somewhatdifferent analysis parameters and conditions than described below inExample 11. The results (analysis in DMF) indicate that the molecularweight of the polymer was M=84,740 g/mol; M_(w)=111,500 g/mol; PDI=1.31,which is a somewhat higher M_(n) than the value of 58,000 g/moldetermined as described below in Example 11. These differing resultsillustrate the well-known sensitivity of polymer molecular weightdeterminations to the specific conditions and methods used for themolecular weight determinations. Thus, the measured molecular weightparameters for the polymers described herein may vary based on thetechniques used to obtain the measurements. The relative GPC molecularweights are believed to be internally consistent and suitable forroutine evaluations due to the relative ease of operation andavailability of equipment, suitable standards, and well developedmethodologies.

Example 5 Poly(Bisphenol A Sulfate) Mechanical Property Evaluation

The bulk polymerization of 2a and 2c was scaled up to 0.5 mole scale.The reaction was performed at 120 OC for 2 hours using 1 mol % BEMPcatalyst. No significant change of internal temperature was observedduring the course of the reaction. BPA-PS with M_(n) 58,000 Da (MALS)was obtained in quantitative yield (145 g). The polymer was mildlysoluble in a wide range of organic solvents including chloroform,dichloromethane, and acetone, while best solubility was observed in DMSOand DMF (about 1 g per 2 mL of DMF, with heating). Treating polysulfatewith 50/50 10% NaOH/EtOH solution at 80 OC for 16 hours caused noobservable change in M_(n), indicating excellent hydrolytic stability incontrast to polycarbonate.

The large scale batch of poly(Bisphenol AA sulfate) was pelletized andcompression-molded for various physical and mechanical analyses. LEXANpolycarbonate samples were compression-molded under similar conditionsand used for comparison. When pressed thin, substantially colorless,transparent and flexible yet stiff films were obtained. Pristine thinfilms/sheets were used for gas permeability measurements. Thickersamples, like those used for tensile strength measurements, exhibited anopaque tan color.

In particular, polysulfate fibers and powder were extruded through amelt flow indexer at 200° C. The thin extrudate was cooled to RT andpelletized by hand with scissors. Polysulfate pellets were compressionmolded into thin films and other sample molds using a Carver press setat 230° C. for 20 minutes total (10 minutes with no pressure, followedby 10 minutes at 25,000 psi). Samples were removed from the press andquenched in water. Tensile dog bones were punched from polysulfateplaques using a sharpened steel “cookie cutter” mold in the Carver pressat room temperature. BPA-polycarbonate (LEXAN) of unspecified grade wasprepared under the same conditions for comparison.

Tensile properties, oxygen permeability, and density were evaluated. Theengineering stress-strain behavior of both polysulfate and polycarbonatepolymers are depicted in FIG. 9. The tensile properties were measuredwith an MTS INSIGHT 10 electromechanical test frame equipped with a 2.5kN load cell. Tests were conducted at ambient temperature in triplicateat a strain rate of 10%/min. The density was determined using theArchimedes method at room temperature with an analytical balance. Masswas averaged over 4 measurements and recorded to 4 decimal places.Density was calculated to 3 decimal places as 1.310 g/cc. The oxygenpermeability of the polymer was determined on a MOCON OX-TRAN 2/21instrument using a continuous-flow testing cell method approved by theASTM (D3985). Measurements were made on two separate BPA-polysulfatefilm samples both at 23° C. and 0% relative humidity (RH). Furtherdetails on this method care described by (a) Sekelik et al., Journal ofPolymer Science Part B: Polymer Physics 1999; 37:847-857; and (b)Kwisnek et al., Macromolecules 2009, 42:7031-7041.

Similar to polycarbonate, the polysulfate exhibited yielding followed byneck formation, stabilization and propagation. Preliminarily, it appearsthat polysulfate has a higher modulus and slightly lower yield stresscompared with the polycarbonate, at least under the specific conditionsused. Strain at break for the polysulfate reached over 50%, but waslimited by sample defects. True elongation may be significantly higher.Yielding and necking were generally atypical for thermoplastic amorphouspolymers at ambient conditions. Polycarbonate and polysulfone are thecommonly used examples. This observation implies that polysulfateexhibited a ductile-to-brittle transition at the stress beyond its yieldstress, a clear indication that this polymer is ductile yet also quiterigid. Larger modulus could be related to less free volume present inpolysulfate at ambient temperatures.

Gas permeability measurements (Table 3) aided in determination of thefree volume. Oxygen permeability for polysulfate surprisingly was foundto be approximately 5 times lower than for polycarbonate, which make thepolysulfates useful in, e.g., packaging applications for oxygensensitive materials. Decreased oxygen permeability may be due to a lowerfree volume. At ambient temperature the polysulfate has less excess holefree volume, stemming from a lower T_(g). BPA-polysulfate exhibited adensity of about 1.310 grams per cubic centimeter (g/cc) or roughly 9%more dense than polycarbonate. Heavy sulfur atoms in the repeat unitcreate a fairly dense material as is common for sulfur-containingpolymers and networks. Practically speaking, polysulfate offers otherpotential advantages over polycarbonate. The lower T_(g) of polysulfatemay ease processing. Also, the basic stability of polysulfate is amarked improvement over polycarbonate which is known to hydrolyze.

TABLE 3 Observed properties of BPA-polysulfate and BPA-polycarbonate(LEXAN) for comparison. Oxygen Permeability Tensile Yield Density at 23°C., 0% RH Modulus Stress Polymer (g/cc) (cm³ m⁻² day⁻¹ atm⁻¹) (GPa)(MPa) Polysulfate 1.310 1.6 1.95 50 Polycarbonate 1.210 9.0 1.66 51

Example 6 Preparation of Poly(Bisphenol A Carbonate)

FIG. 10 provides a schematic illustration of the preparation of abisphenol A polycarbonate polymer by the methods described herein.Fluorophosgene (COF₂) was generated from bis-trichloromethyl carbonate(“triphosgene”) with potassium fluoride and 1.5 percent 18-crown-6 inacetonitrile according to the method described by Olofson, TetrahedronLetters, 2002; 34:4275-4279. In particular, a solution of 18-crown-6(200 mg) in acetonitrile (5 mL) was added dropwise into a stirringmixture of triphosgene (2 g, 6.8 mmol) and spray-dried KF (3.23 g, 55mmol) in acetonitrile (30 mL) in a flask cooled by an ice-water bath.The flask was fitted with a dry ice/acetone cold finger condenser, andthe generated COF₂ gas was passed into a reaction vessel containing a 1M solution of bis-trimethylsilyl-bisphenol A (about 1 gram total) inNMP. About 0.1 mL of DBU was introduced into the NMP solution bysyringe. The solution immediately turned deep purple upon addition ofthe DBU. The resulting mixture was stirred at ambient room temperature(about 20 to 22° C.) for about 12 hours. The reaction mixture formed asticky gel, which was diluted in methanol to form grey, fibrouspoly(bisphenol A carbonate) in approximately quantitative yield (about690 mg). The polycarbonate was analyzed by GPC relative to polystyrenestandards, which indicated a M_(w) of about 159860, and a M_(n) of about70539 (PDI of about 2.27).

Example 7 Additional Polymerization Examples

Various difunctional phenols underwent end-group transformation andpolymerization following a reaction scheme similar to the one shown inFIG. 2. Trifluoromethylated BPA monomers were used to form homopolymersand copolymers of good quality and high molecular weight.

The compatibility of the polymerization reaction with differentfunctional groups was examined. Monomers 4-13 were prepared according toprocedures similar to those illustrated in FIG. 2 and included BisphenolAF (4a/b), naphthalene (5a/b), ether (6a/c), ester (9a/c and 12c),sulfide (8a/c), ketone (9a/c), amide (10a/c and 13c), and bisphenol S(sulfone, 11a/c) derivatives. The polymerization reaction was conductedat room temperature in 1M NMP with 20 mol % of DBU for 24 hrs. As Table4 illustrates, a variety of homopolymers and BPA copolymers wereobtained, demonstrating compatibility of the reaction with differentfunctional groups. The observed molecular weights, as referenced topolystyrene standards, were in the same general range, which does notallow for conclusions to be drawn about relative reactivity of differentmonomer families. Among BPA-copolymers of similar structure, molecularweight decreased when para electron donating (cf. Entry 5 vs. 6, 11 vs.12 in Table 4) or withdrawing (cf. Entry 8 vs. 9, 14 vs. 15) groups werepresent in the silyl ether monomer. The selectivity of the reaction isdemonstrated by the successful formation of co-polysulfates containingtechnologically useful blocks found in other engineering polymers.Polymers were also obtained from bis-sulfonyl fluorides (Entry 23). Thesulfonyl fluoride monomer 14 was directly obtained from 4,4′-biphenylbis-sulfonyl chloride via a facile transformation using saturatedaqueous KHF₂ solution in acetonitrile at room temperature.

TABLE 4 Entry Structure Monmers M_(n) ^(PS) PDI 1 2

R = OSO₂F  = OTMS (4a) (4b) 4a + 4b 4a + 2b 46,100 36,000 1.5 1.4 3

R = OSO₂F  = OTMS (5a) (5b) 5a + 5b 52,000^([b]) 1.6 4 5 6

R = OSO₂F  = OTBS (6a) (6c) 6a + 6c 6a + 2c 2a + 6c 58,700 67,100 46,6001.4 1.4 1.4 7 8 9

R = OSO₂F  = OTBS (7a) (7c) 7a + 6c 7a + 2c 2a + 7c 34,700 37,200 30,6001.5 1.5 1.5 10 11 12

R = OSO₂F  = OTBS (8a) (8c) 8a + 6c 8a + 2c 2a + 8c 80,100 52,500 36,9001.4 1.5 1.4 13 14 15

R = OSO₂F  = OTBS (9a) (9c) 9a + 6c 9a + 2c 2a + 9c 34,100^([c]) 41,10021,800^([d]) 1.6 1.6 1.4 16 17 18

R = OSO₂F  = OTBS (10a) (10c) 10a + 6c 10a + 2b  2a + 10c 81,100 48,70075,400 1.4 1.3 1.4 19 20

R = OSO₂F  = OTBS (11a) (11c) 11a + 11c 11a + 2c 22,100^([d]) 24,800 1.31.3 21

R = OTBS (12c) 2a + 12c 53,000 1.5 22

R = OTBS (13c) 2a + 13c 43,900 1.4 23

R = SO₂F (14) 14 + 2c 46,500 1.3 Notes for Table 4: ^([a])polymerizationat 80° C.; ^([b])increasing temperature to 100° C. afforded a GPC M_(n)of 46,100 and a PDI of 1.5; ^([c])oligomeric product; ^([d])increasingthe temperature to 100° C. afforded a GPC M_(n) of 43,200 and a PDI of1.4.

FIG. 11 provides a representative sampling of sulfonyl and sulfatepolymer structures prepared by the methods described herein. In additionto providing a practical route to polymers with useful properties anddiverse structural elements, the exceptionally facile synthesis ofpoly(organosulfates) described here highlights the underappreciatedpotential of the sulfate connector in organic and materials chemistry aswell as unique reactivity features of sulfur(VI) oxofluorides. This newclick reaction should find immediate applications across differentdisciplines.

Example 8 Effects of Monomer Stoichiometry

The excess of both silyl ether-functional and fluorosulfate-functionalBPA monomers was varied from 0.0, or no mismatch, gradually up to 1.0,or a 100% stoichiometric imbalance in order to probe the effect ofmismatches in stoichiometry when either the bis-silyl ether or thebis-fluorosulfate 2a were in excess. These results are summarized inTable 5. Excess silyl ether, in this case the bis-OTBS BPA monomer 2c,resulted in decreases in both M and PDI, based on GPC. This decrease inM_(n) was expected due to conventional step-growth rules. Yields over90% were obtained in almost each case, indicative of completeconsumption of the limiting monomer. At 1.0 molar excess, the yield wasnoticeably lower due to the loss of lower oligomers duringprecipitation. In the case of excess fluorosulfate monomer, a completelydifferent effect was observed. For a 0.05 molar excess ofbis-fluorosulfate, the M_(n) was on par or better than thenon-mismatched control system. The M_(n) then proceeded to decrease fromthis maximum as further excess of the bis-fluorosulfate was used. Ineach case, however, the M_(n) was higher than for the same molarequivalent excess of bis-silyl ether. Yields also curiously increased,reaching over 100% for polymerizations with the largest excess ofbis-fluorosulfate. Thus it is evident for this polymerization that while“A-A” (bis-fluorosulfate) primarily reacts with “B-B” (bis-silyl ether),A-A also can react with A-A. Not only is this result a strikingexception to traditional step-growth polymerization rules, the polymersobtained also appear to be fluorosulfate functional on both ends oflinear polymer chains. In the case of traditional step-growthengineering polymers, the end groups often are statistical mixtures of Aor B functionality. These groups are then either end-capped withmonofunctional reagents, or are simply degraded or too weakly reactiveto be useful. Ensuring stable, click-ready functional groups on the endsof a step-growth polymer without any extra manipulation or tedioustransformations is one important goal for engineering polymers.

TABLE 5 BPA-polysulfate Tolerance to Stoichiometric Imbalance. 2c (TBS)excess 2a (OSO₂F) excess Entry Equiv. yield M_(n) PDI yield M_(n) PDI 10.00 94% 65,500 1.8 2 0.05 91% 38,800 1.6  90% 71,300 1.6 3 0.10 94%31,100 1.5  91% 40,300 1.5 4 0.25 99% 18,400 1.5 102% 22,500 1.4 5 0.5093% 13,400 1.4 110% 16,200 1.3 6 1.00 61% 9,300 1.2 120% 12,300 1.2

Example 9 Polymer End Group Modification

About 200 mg of poly(bisphenol A sulfate) having a GPC M_(n) of about71,000 g/mol prepared in Example 8 (Entry 2 from Table 5) was dissolvedin about 4 mL of DMF along with about 100 mg of TBS-protected Nile Reddye and about 20 microliters of DBU as shown in FIG. 12. The mixture wasstirred at about 40° C. for about 1.5 hours to afford polymer comprisingNile Red dyes attached at the polymer end groups. The dyed polymer wasprecipitated by dilution with about 20 mL of methanol. The resultingprecipitated polymer had a characteristic magenta color due to the NileRed end groups. Covalent attachment of the dye to the polymer wasverified by re-dissolving a sample of the dyed polymer in DMF andperforming a GPC separation using UV-Vis detection at multiplewavelengths from 200 to 800 nm. The GPC traces showed that the trace at567 nm detector wavelength exhibited a peak at the same elution time aswhen the polymer backbone wavelength (203 nm) was used. Dye attachmentto the polymer also was verified by comparison of the UV-visiblespectrum of the silylated Nile Red dye with the dyed polymer and amonomeric material comprising a single Nile Red molecule attached via asulfate linkage to a single bisphenol A compound (see FIG. 13). Thepolymer and the bisphenol A-Nile Red conjugated compound had virtuallyidentical UV/Vis spectra, whereas the spectrum of silylated Nile Red wasshifted hypsochromically relative to the dyed polymer and dyed monomermaterials (see FIG. 14). Thus, the ability to covalently attach the dyeto the polymer confirms the presence of fluorosulfate end groups on thepolymer.

Example 10 Fluorine NMR End Group Analysis

¹⁹F NMR end group analysis was utilized to obtain an independentapproximation of the degree of polymerization (DP) and thus M_(n), forpoly(bisphenol AF sulfate).

These polymer samples were prepared in NMP as solvent and then dissolvedin d7-DMF for NMR analysis. Experiments with monomer mixtures verifiedthat the sensitivity for quantifying the end group signal for OSO₂Frelative to the polymer chain CF₃ signal was at least about 1:600 (bypeak integration), which corresponds to a DP (n) of about 200 assumingall of the polymer is linear and includes two OSO₂F end groups.Reactions were performed at about 1M concentration in NMP withbis(t-butyldimethylsilyl)bisphenol AF and excessbis(fluorosulfonyl)bisphenol AF in the presence of DBU as catalyst atambient room temperature for about 16 hours. Experiments were run withfive different amounts of the bis(fluorosulfonyl)bisphenol AF (5 mol %,10 mol %, 20 mol %, 50 mol %, and 100 mol % excess). The DP valuesobtained from these evaluations are upper limits, since the presence ofany cyclic polymer/oligomer can skew the results to higher apparent DP.A 5 mol % excess bis(fluorosulfonyl)bisphenol AF afforded a DP of >200(M_(n)>about 78000 g/mol), i.e., no detectible end group signal; a 10mol % excess afforded DP of about 90 (M_(n) of about 35100); a 20 mol %excess afforded DP of about 26 (M_(n) of about 10140), a 50 mol % excessafforded DP of about 13 (M_(n) of about 5070), and a 100 mol % excessafforded DP of about 7 (M_(n) of about 2730). A bulk-prepared sample ofthe polymer (no solvent) did not exhibit any detectible OSO₂F end groupsignal, indicating a DP of >200 and/or potentially a large cyclicstructure.

Example 11 Detailed Description of Monomer and Polymer Syntheses Ex. 11AMaterials and Methods

¹H and ¹³C NMR spectra were recorded on AMX-400 (Bruker) and INOVA-400(Varian) instruments at 295 K unless otherwise noted. Chemical shifts(δ) are expressed in parts per million relative to residual CHCl₃,acetone, or DMSO as internal standards. Proton magnetic resonance (¹HNMR) spectra were recorded at 400 MHz. Carbon magnetic resonance (¹³CNMR) spectra were recorded at 100 MHz. Abbreviations are: s, singlet; d,doublet; t, triplet; q, quartet; p, pentet; sex, sextet; sept, septet;app, apparent. Infrared spectra were recorded on an AVATAR 370 Fouriertransform infrared spectrometer (ThermoNicolet) and are expressed inwavenumbers (cm⁻¹). Melting points (mp) were determined using a meltingpoint apparatus (Thomas-Hoover) and are uncorrected. GCMS data wererecorded on a 7890A GC system (Agilent) with a 5975C Inert MSD system(Agilent) operating in electron impact (EI+) mode [T_(o)=50° C. for 2.25minutes; ramp to 300° C. at 60° C./min; hold at 300° C. for 4 minutes].HPLC analysis was performed on a 1100 LC/MSD (Agilent) with a 1100 SLmass spectrometer (Agilent; electrospray ionization, ES) eluting with0.1% trifluoroacetic acid in H₂O and 0.05% trifluoroacetic acid inCH₃CN. Precoated F-254 silica gel plates (Merck) were used for thinlayer analytical chromatography (TLC) and visualized with short wave UVlight or by potassium permanganate stain. Column chromatography wascarried out employing EMD (Merck) Silica Gel 60 (40-63 μm). GPC analysiswas carried out on a LC20 HPLC system (Shimadzu) equipped with adiode-array and a refractive index detector, and STYRAGEL HR-3 and HR-4columns (Waters; 5 μm particle size, 7.2 mm diameter) connected inseries and placed in a column oven. The system was calibrated withREADYCAL polystyrene standards, M_(n) range 500 g/mol to 600,000 g/mol),eluting with HPLC grade DMF with 0.1% (wt.) of LiBr as a modifier. Theaccuracy of calibration was verified at regular intervals. A MINIDAWNTREOS detector (Wyatt) was used for multi-angle light scattering (MALS)analysis. Unless otherwise noted, all starting materials and solventswere purchased from Aldrich, Acros Organics, Fisher, TCI, Alfa Aesar orStrem Chemicals and used as received. Dimethylformamide (DMF) andN-methyl-2-pyrrolidone (NMP) were obtained as “99.5% Extra Dry overMolecular Sieves” from Acros Organics.1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) was obtained from Alfa Aesarand used as received.2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaza-phosphorine(BEMP) was obtained from Sigma Aldrich as a 1M solution in hexanes.Sulfuryl fluoride gas (SO₂F₂, commercially produced under the trade nameVIKANE) was a gift from Dow Agro.

Ex. 11B General Polymerization Procedures

(a) Small Scale Bulk Polymerization—(See Table 2).

A-A (2a; 1-5 mmol) and B-B (2b-e; 1-5 mmol) monomers were combined in a16 mL thick glass-walled, screw capped vessel containing a Teflon-coatedmagnetic stir bar and sealed with a PTFE/Silicone septum. This reactorwas then placed into a 150° C. oil bath with stirring, and once themonomers melted, catalyst was introduced to initiate polymerization.Heating was continued for 2 hours, at which point the solidified mixturewas cooled and diluted with about 1-2 mL DMF per 1 g of polymer.Dissolution was assisted by vigorous heating with a heat gun or byre-introduction to the 150° C. oil bath. Once fully dissolved, the DMFsolution was poured into about 100 mL of methanol per 1 g of polymer toprecipitate white BPA-polysulfate as a either a fiber or powderdepending on molecular weight. The obtained polymers were then dried at65° C. in a vacuum oven and subjected to GPC analysis.

(b) Monomer Structure Tolerance in the Polymerization Reaction—(SeeTable 4).

Pairs of bis(fluorosulfate) (4-11a and 14; 1-3 mmol) and bis(silylether) monomers (TMS 2b, 4b-5b and TBS 2c, 6-13c; 1-3 mmol) werecombined in 16 mL thick glass-walled screw-capped vessels equipped withTeflon-coated magnetic stir bars and sealed with a PTFE/Silicone septa.These mixtures were dissolved in 1 mL of NMP per 1 mmol substrate (about1 M solution with respect to each monomer) and treated with 20 mol % ofDBU. Stirring was continued for 24 hour at room temperature. Thereaction mixtures were then heated with a heat gun to dissolve anyprecipitated polymer and the resulting homogenous solution (in somecases additional DMF was necessary to achieve complete dissolution) wasadded directly to about 100 mL of methanol per 1 g of polymer at ambienttemperature to precipitate the polysulfate copolymers.

-   -   (c) Molecular Weight Determinations.

GPC was used to determine number average molecular weight (M_(n)),weight average molecular weight (M_(w)), and polydispersity index (PDI).The system was calibrated using narrow molecular weight polystyrenestandards. For several samples, multi-angle light scattering wasdetermined using a MINIDAWN TREOS detector (Wyatt). Mobile phase wasHPLC grade DMF with 0.1% (wt.) of LiBr modifier. Representative GPCtraces and MALS analysis reports are provided for the key polymersamples in Table 6.

TABLE 6 (Letter designations from Table 2) PS Standards MALS Conditions:M_(n) (g/mol) M_(n) (g/mol) Dispersity Bulk (TMS, 1% BEMP) (A) 17,0002,500 1.3 Bulk (TMS, 20% DBU) (B) 38,000 10,600 1.4 Bulk (TBS, 20% DBU)(C) 66,000 19,600 1.4 Bulk (TBS, 1% BEMP) (D) 120,000 58,000 1.7

For the MALS analysis, the differential index of refraction (dn/dc) wasdetermined using batch method by plotting the refractive index of thepolymer solution versus varying solution concentrations. The mobilephased used to dissolve BPA-polysulfate (“sample D”, Mn=120,000 Da basedon polystyrene standards) for dn/dc determination and subsequent MALSanalysis was HPLC grade DMF with 0.1% LiBr (wt.). The dn/dc was obtainedin duplicate. In Run #1, the dn/dc was determined to be 0.13009. In Run#2 the dn/dc was determined to be 0.12623 (see Table 7 and FIG. 14,Panels (a)—Run #1, and Panel (b)—Run #2.

TABLE 7 Run #1 Run #2 Polysulfate Refractive Polysulfate RefractiveConc. Index Conc. Index Entry (mg/mL) (mv) (mg/mL) (mv) 1 1.22 144 0.7484 2 1.77 236 1.38 203 3 2.27 306 1.84 248 4 3.04 420 2.77 381 5 4.42556 3.68 475 6 5.67 736 4.50 593 7 6.14 755 8 6.92 848

Ex. 11C Monomer Preparations

An illustrative general procedure for the preparation of thebis-fluorosulfate “AA” monomers used in Table 4 is provided below (i.e.,the preparation of Compound 2a).

4,4′-(Propane-2,2-diyl)bis(4,1-phenylene)disulfofluoridate (2a).Bisphenol A (1; 20 g, 0.088 mol) and triethylamine (30 mL, 21.8 g, 0.216mol) were dissolved in CH₂Cl₂ (200 mL) in a 500 mL round bottom flaskequipped with a stirring bar. The headspace of the reaction vessel wasevacuated and filled with sulfuryl fluoride gas introduced via a needleattached to a balloon. The reaction was stirred at room temperature for12 hours, at which time GC-MS analysis indicated complete conversion.The reaction mixture was then concentrated in vacuo, re-dissolved in 300mL of EtOAc and washed sequentially with 300 mL of 0.6M HCl (1×), 200 mLsat. NaHCO₃ (1×), 200 mL sat. NaCl (1×), and dried over Na₂SO₄. Removalof the volatiles produced 2a as a yellow oil that crystallized as awhite solid that was subsequently dried under vacuum (33.3 g, 84.9 mmol,98%): mp 49-52° C.; IR (neat) λ_(max) 1499, 1441, 1409, 1368, 1229,1186, 1137, 1083, 1015, 949, 911, 840, 812, 793, 772, 599, 564, 538,502, 472 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.32-7.25 (m, 8H), 1.71 (s,6H); ¹³C NMR (100 MHz, CDCl₃) δ 150.6, 148.4, 128.9, 120.7, 43.1, 30.9;¹⁹F NMR (376 MHz, CDCl₃) δ 37.2; GC-MS (EI) m/z=392.1 [M]⁺.

An illustrative general procedure for the preparation of the bis-silyl“BB” monomers used in Table 4 is presented below (i.e., the preparationof Compound 2c). Note that HCl wash used Compound 2c is replaced with anadditional NaHCO₃ wash for the preparation of trimethylsilyl monomers).

(4,4′-(Propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(tert-butyldimethylsilane)(2c).

Bisphenol A (1; 50 g, 0.219 mol), imidazole (45 g, 0.662 mol) and4-dimethylaminopyridine (1.3 g, 0.11 mol) were dissolved in a mixture of500 mL of CH₂Cl₂ and 40 mL of dimethylforamide in a 3 L round bottomflask equipped with a stirring bar. tert-Butyldimethylsilyl chloride (69g, 0.46 mol) was added portion-wise to the reaction, which quicklyresulted in the generation of a white precipitate. The reaction mixturewas stirred for 3 h, filtered to remove all solids (imidazole-HCl) andconcentrated in vacuo. The resulting oil was dissolved in 750 mL ofEtOAc and sequentially washed with 700 mL of 1M HCl (1×), 400 mL sat.NaHCO₃ (1×), 500 mL sat. NaCl (1×) and then dried over Na₂SO₄.). Removalof the volatiles gave 2c as a colorless oil that crystallized as acolorless solid and was subsequently dried under vacuum (96.3 g, 0.211mmol, 96%): mp 84-87° C.; IR (neat) λ_(max) 2953, 1501, 1441, 1230,1184, 1137, 1015, 911, 828, 810, 773, 592, 563, 539 cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 7.07 (d, J=8.8 Hz, 4H), 6.72 (d, J=8.8 Hz, 4H), 1.62 (s,6H), 0.98 (s, 18H), 0.19 (s, 12H); ¹³C NMR (100 MHz, CDCl₃) δ 153.4,143.8, 127.8, 119.3, 41.9, 31.2, 25.8, 18.3, −4.3; GC-MS (EI) m/z=456.4[M]⁺.

(4,4′-(Propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(trimethylsilane)(2b) was purchased from Gelest, Inc. and used as received.

(4,4′-(Propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(tert-butyldiphenylsilane)(2d) was prepared from(4,4′-(propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(trimethylsilane)following the general procedure for the preparation of bis-silyl “BB”monomers, with substitution of tert-butyldimethylsilyl chloride withtert-butyldiphenylsilyl chloride. Purification via flash chromatography(SiO₂, 0-5% EtOAc-hexanes; R_(f)=0.5 at 10% EtOAc-hexanes) yielded 2d asa white crystalline solid (about 27.8 g, 39.4 mmol, 90%): mp 94-98° C.;IR (neat) λ_(max) 1501, 1442, 1230, 1164, 1138, 913, 822, 797, 773, 742,700, 594, 563, 541, 502 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.86 (dd, J=1.6,8.0 Hz, 8H), 7.57-7.38 (m, 12H), 7.01 (d, J=8.9 Hz, 4H), 6.79 (d, J=8.8Hz, 4H), 1.63 (s, 6H), 1.25 (s, 18H); ¹³C NMR (100 MHz, CDCl₃) δ 153.4,143.6, 135.7, 133.3, 129.9, 127.8, 127.6, 119.0, 41.7, 31.1, 26.7, 19.6;

(4,4′-(Propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(triisopropylsilane)(2e) was prepared from(4,4′-(propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(trimethylsilane)following the general procedure for the preparation of bis-silyl “BB”monomers, with substitution of tert-butyldimethylsilyl chloride withtriisopropylsilyl chloride. 2e was isolated as a colorless, viscous oil(23.1 g, 42.5 mmol, 97%): IR (neat) λ_(max) 2943, 2864, 1604, 1504,1462, 1257, 1176, 1106, 1012, 912, 882, 833, 743, 680, 609, 559, 482cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.07 (d, J=8.7 Hz, 4H), 6.79 (d, J=8.7Hz, 4H), 1.64 (s, 6H), 1.36-1.18 (m, 6H), 1.13 (d, J=7.2 Hz, 36H); ¹³CNMR (100 MHz, CDCl₃) δ 153.8, 143.7, 127.8, 119.3, 41.9, 31.3, 18.1,12.8; LRMS (EI) m/z=497.4 [M-CH(CH₃)₂]⁺.

Bisphenol AF (2,2-bis(4-hydroxyphenol)hexafluoropropane) was obtainedfrom Oakwood Chemicals and used as received.

4,4′-(Perfluoropropane-2,2-diyl)bis(4,1-phenylene)disulfofluoridate (4a)was prepared from Bisphenol AF following the general procedure for thepreparation of bis-fluorosulfate “AA” monomers. 4a was isolated as whitecrystalline solid: mp 128-130° C.; IR (neat) λ_(max) 1506, 1450, 1261,1240, 1208, 1163, 1144, 1019, 968, 911, 840, 805, 768, 737, 697, 645,575, 536 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.53 (app d, J=9.0 Hz, 4H),7.42 (dd, J=0.6, 9.2 Hz, 4H); ¹³C NMR (100 MHz, CDCl₃) δ 150.4, 133.6,132.6, 123.7 (q, J=E287.5 Hz), 121.3, 64.2 (app t, J=25.8 Hz); ¹⁹F NMR(376 MHz, CDCl₃) δ 38.2, −64.1; LRMS (EI) m/z=500.0 [M]⁺.

(4,4′-(Perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(trimethylsilane)(4b) was prepared from Bisphenol AF following the general procedure forthe preparation of bis-silyl “BB” monomers, with substitution oftert-butyldimethylsilyl chloride with trimethylsilyl chloride andomitting the HCl wash. 4b was isolated as a beige solid: mp 46-50° C.;IR (neat) λ_(max) 2959, 1611, 1513, 1450, 1242, 1204, 1168, 1135, 967,912, 828, 753, 737, 700, 545, 505 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.25(d, J=9.2 Hz, 4H), 6.81 (d, J=9.1 Hz, 4H), 0.29 (s, 4H); ¹³C NMR (100MHz, CDCl₃) δ 155.9, 131.7, 126.4, 124.6 (q, J=287.8 Hz), 119.6, 63.9(t, J=25.5 Hz), −0.32; ¹⁹F NMR (376 MHz, CDCl₃) δ −64.4; LRMS (EI)m/z=480.2 [M]⁺.

(4,4′-(Perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy)bis(tert-butyldimethylsilane)4c was prepared from Bisphenol AF following the general procedure forthe preparation of bis-silyl “BB” monomers. 4c was isolated as a whitecrystalline solid: mp 167-170° C.; IR (neat) λ_(max) 2952, 2932, 2859,1611, 1513, 1468, 1275, 1244, 1202, 1168, 1134, 968, 911, 830, 804, 777,727, 701, 667, 556 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.24 (d, J=8.7, 4H),6.80 (d, J=9.0 Hz, 4H), 0.99 (s, 18H), 0.23 (s, 12H); ¹³C NMR (100 MHz,CDCl₃) δ 156.2, 131.7, 126.3, 124.6 (app d, J=285.1 Hz), 119.6, 63.8 (t,J=25.2 Hz), 25.8, 18.3, −4.3; ¹⁹F NMR (376 MHz, CDCl₃) δ −64.4; LRMS(EI) m/z=451.0 [M-Si(Me)₂t-Bu]⁺.

Naphthalene-2,7-diol was purchased from Acros Organics and used asreceived.

Naphthalene-2,7-diyl disulfofluoridate 5a was prepared fromnaphthalene-2,7-diol following the general procedure for the preparationof bis-fluorosulfate “AA” monomers. 5a was isolated as white powder(12.3 g, 38 mmol, 87%): mp 122-124° C.; IR (neat) λ_(max) 1439, 1365,1219, 1187, 1137, 1115, 960, 922, 896, 839, 801, 637, 582, 530, 470cm⁻¹; ¹H NMR (400 MHz, DMSO-d₆) δ 8.36 (d, J=2.2 Hz, 2H), 8.28 (d, J=9.1Hz, 2H), 7.82 (dd, J=2.4, 9.1 Hz, 2H); ¹³C NMR (100 MHz, DMSO-d₆) δ148.3, 133.3, 131.6, 120.9, 119.5; ¹⁹F NMR (376 MHz, DMSO-d₆) δ 38.1;LRMS (EI) m/z=324.0 [M]⁺.

2,7-Bis(trimethylsilyloxy)naphthalene 5b was prepared fromnaphthalene-2,7-diol following the general procedure for the preparationof bis-silyl “BB” monomers, with substitution of tert-butyldimethylsilylchloride with trimethylsilyl chloride. 5b was isolated as a yellow oil(13.1 g, 43.5 mmol, 99%): IR (neat) λ_(max) 2958, 2856, 1630, 1604,1507, 1460, 1427, 1365, 1250, 1211, 1151, 1110, 909, 833, 743, 697, 612,489 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.69 (d, J=8.9 Hz, 2H), 7.12 (d,J=2.3 Hz, 2H), 6.99 (dd, J=2.3, 8.8 Hz, 2H), 0.37 (s, 18H); ¹³C NMR (100MHz, CDCl₃) δ 153.6, 136.2, 129.3, 125.4, 120.0, 114.0, −0.42; LRMS (EI)m/z=304.1 [M]⁺.

4,4′-Oxydiphenol was purchased from AK Scientific and used as received.

4,4′-Oxybis(4,1-phenylene)disulfofluoridate 6a was prepared from4,4′-oxydiphenol following the general procedure for the preparation ofbis-fluorosulfate “AA” monomers. 6a was isolated as white crystallinesolid (8.2 g, 22.5 mmol, 75%): mp 53-55° C.; IR (neat) λ_(ax) 1499,1443, 1230, 1162, 1132, 1100, 909, 839, 818, 768, 754, 602, 540, 501cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.36 (dtd, J=0.9, 3.7, 10.6 Hz, 4H),7.11 (dt, J=3.7, 9.3 Hz, 4H); ¹³C NMR (100 MHz, CDCl₃) δ 156.4, 145.8,122.9, 120.6; ¹⁹F NMR (376 MHz, CDCl₃) δ 36.9; LRMS (EI) m/z=366.0 [M]⁺.

(4,4′-Oxybis(4,1-phenylene)bis(oxy))bis(tert-butyldimethylsilane) (6c)was prepared from 4,4′-oxydiphenol following the general procedure forthe preparation of bis-silyl “BB” monomers. 6c was isolated as a clear,colorless, viscous oil (11.9 g, 27.8 mmol, 93%): IR (neat) λ_(max) 2930,2857, 1491, 1451, 1251, 1213, 1144, 1096, 908, 871, 835, 778, 691, 504cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 6.89-6.82 (m, 4H), 6.80-6.77 (m, 4H),0.99 (s, 18H), 0.19 (s, 12H); ¹³C NMR (100 MHz, CDCl₃) δ 152.1, 151.3,120.9, 119.6, 25.8, 18.3, −4.3; LRMS (EI) m/z=430.3 [M]⁺.

4-Hydroxyphenyl 4-hydroxybenzoate was prepared through the condensationof hydroquinone with 4-hydroxybenzoic acid as described by Goldfinger etal. in WO2009023759 A2.

4-(Fluorosulfonyloxy)phenyl 4-(fluorosulfonyloxy)benzoate (7a) wasprepared from 4-hydroxyphenyl 4-hydroxybenzoate following the generalprocedure for the preparation of bis-fluorosulfate “AA” monomers.Purification via flash chromatography (SiO₂, 5→15% EtOAc-hexanes;R_(f)=0.52 at 20% EtOAc-hexanes) yielded 7a as a white powder (1.77 g,4.5 mmol, 45%): mp 103-105° C.; IR (neat) λ_(max) 1740, 1497, 1443,1260, 1230, 1135, 1068, 1015, 909, 801, 757, 689, 612, 540, 491 cm⁻¹; ¹HNMR (400 MHz, CDCl₃) δ 8.34 (d, J=9.0 Hz, 1H), 7.52 (dd, J=0.7, 9.0,1H), 7.47-7.40 (m, 1H), 7.36 (d, J=9.3 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃)δ 163.2, 153.6, 150.3, 147.5, 132.9, 129.5, 123.7, 122.5, 121.5; ¹⁹F NMR(376 MHz, CDCl₃) δ 38.8, 37.24; LRMS (EI) m/z=393.8 [M]⁺.

4-(tert-butyldimethylsilyloxy)phenyl4-(tert-butyldimethylsilyloxy)benzoate (7c) was prepared from4-hydroxyphenyl 4-hydroxybenzoate following the general procedure forthe preparation of bis-silyl “BB” monomers. Purification via flashchromatography (SiO₂, 2% EtOAc-hexanes; R_(f)=0.56 at 5% EtOAc-hexanes)yielded 7c as a white powder (2.05 g, 4.4 mmol, 45%): mp 69-73° C.; IR(neat) λ_(max) 2956, 2928, 2857, 1737, 1601, 1501, 1442, 1252, 1232,1187, 1160, 1067, 1010, 904, 822, 782, 692, 540, 501 cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 8.10 (d, J=8.9 Hz, 2H), 7.06 (d, J=9.0 Hz, 2H), 6.93 (d,J=8.9 Hz, 2H), 6.87 (d, J=9.0 Hz, 2H), 1.01 (s, 9H), 1.00 (s, 9H), 0.26(s, 6H), 0.22 (s, 6H); ¹³C NMR (100 MHz, CDCl₃) δ 165.3, 160.7, 153.3,145.2, 132.3, 122.8, 122.6, 120.7, 120.2, 25.8, 25.8, 18.4, 18.3, −4.2,−4.3; LRMS (EI) m/z=458.2 [M]⁺.

4,4′-Thiodiphenol was purchased from Alfa Aesar and used as received.

4,4′-Thiobis(4,1-phenylene)disulfofluoridate (8a) was prepared from4,4′-thiodiphenol following the general procedure for the preparation ofbis-fluorosulfate “AA” monomers. 8a was isolated as off-whitecrystalline solid (17.1 g, 44.7 mmol, 98%): mp 54-56° C.; IR (neat)λ_(max) 1485, 1442, 1230, 1177, 1139, 1101, 1014, 909, 835, 803, 769,581, 540, 496 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.44 (d, J=9.0 Hz, 4H),7.32 (dd, J=0.9, 9.0 Hz, 4H); ¹³C NMR (100 MHz, CDCl₃) δ 149.3, 136.2,133.0, 122.2; ¹⁹F NMR (376 MHz, CDCl₃) δ 37.7; LRMS (EI) m/z=382.0 [M]⁺.

(4,4′-Thiobis(4,1-phenylene)bis(oxy))bis(tert-butyldimethylsilane) (9c)was prepared from 4,4′-thiodiphenol following the general procedure forthe preparation of bis-silyl “BB” monomers. 9c was isolated as a clear,colorless, viscous oil (20.3 g, 46 mmol, 99%): IR (neat) λ_(max) 2929,2856, 1586, 1485, 1444, 1254, 1231, 1140, 1072, 1013, 907, 821, 804,772, 739, 673, 585, 521, 498 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.20 (d,J=8.7 Hz, 2H), 6.77 (d, J=8.7 Hz, 2H), 0.98 (s, 9H), 0.19 (s, 6H); ¹³CNMR (100 MHz, CDCl₃) δ 155.2, 132.7, 128.1, 121.0, 25.8, 18.3, −4.3;LRMS (EI) m/z=446.3 [M]⁺.

Bis(4-hydroxyphenyl)methanone was purchased from AK Scientific and usedas received.

4,4′-Carbonylbis(4,1-phenylene)disulfofluoridate (9a) was prepared frombis(4-hydroxyphenyl)methanone following the general procedure for thepreparation of bis-fluorosulfate “AA” monomers. 9a was isolated as whitecrystalline solid (11.1 g, 29.3 mmol, 98%): mp 91-94° C.; IR (neat)λ_(max) 1672, 1591, 1440, 1409, 1268, 1231, 1138, 1015, 907, 808, 761,667, 632, 540, 494, 466 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.97-7.87 (m,4H), 7.60-7.45 (m, 4H); ¹³C NMR (100 MHz, CDCl₃) δ 192.8, 152.7, 137.0,132.3, 121.3; ¹⁹F NMR (376 MHz, CDCl₃) δ 38.6; LRMS (EI) m/z=378.0 [M]⁺.

Bis(4-(tert-butyldimethylsilyloxy)phenyl)methanone (9c) was preparedfrom bis(4-hydroxyphenyl)methanone following the general procedure forthe preparation of bis-silyl “BB” monomers. 9c was isolated as acolorless low melting solid (13.3 g, 30 mmol, 99%): IR (neat) λ_(max)2960, 2930, 2857, 1651, 1596, 1505, 1466, 1254, 1160, 1105, 904, 836,803, 773, 713, 682, 494 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.73 (app d,J=8.8 Hz, 4H), 6.90 (app d), J=8.8 Hz, 4H), 1.00 (s, 18H), 0.25 (s,12H); ¹³C NMR (100 MHz, CDCl₃) δ 194.9, 159.7, 132.3, 131.4, 119.8,25.7, 18.4, −4.2; LRMS (EI) m/z=442.3 [M]⁺.

4-Hydroxy-(4-hydroxyphenyl)benzamide was prepared in four steps fromwith 4-hydroxybenzoic acid and 4-aminophenol as described by (a) C. H.Rohrig, C. Loch, J.-Y. Guan, G. Siegal, M. Overhand, ChemMedChem 2007,2, 1054-1070; (b) P. W. Elsinghorst, J. S. Cieslik, K. Mohr, C. Tränkle,M. Gütschow, Journal of Medicinal Chemistry 2007, 50, 5685-5695.

4-(Fluorosulfonyloxy)-N-(4-(fluorosulfonyloxy)phenyl)benzamide (10a) wasprepared from 4-hydroxy-(4-hydroxyphenyl)benzamide following the generalprocedure for the preparation of bis-fluorosulfate “AA” monomers.Purification via flash chromatography yielded 10a as a white powder(1.86 g, 4.7 mmol, 50%): mp 160-167° C.; IR (neat) λ_(max) 3417, 1677,1600, 1524, 1503, 1437, 1405, 1309, 1258, 1225, 1176, 1138, 1104, 1018,910, 864, 849, 833, 804, 775, 694, 616, 542, 510, 469 cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 10.70 (s, 1H), 8.15 (d, J=8.9 Hz, 2H), 7.96 (d, J=9.3 Hz,2H), 7.80 (d, J=8.6 Hz, 2H), 7.60 (d, J=9.0 Hz, 2H); ¹³C NMR (100 MHz,CDCl₃) δ 164.5, 151.5, 145.2, 139.5, 135.4, 130.6, 121.9, 121.4; ¹⁹F NMR(376 MHz, CDCl₃) δ 39.6, 38.27; LRMS (EI) m/z=393.0 [M]⁺.

4-(tert-Butyldimethylsilyloxy)-N-(4-(tert-butyldimethylsilyloxy)phenyl)benzamide(10c) was prepared from 4-hydroxy-(4-hydroxyphenyl)benzamide followingthe general procedure for the preparation of bis-silyl “BB” monomers.Purification via flash chromatography yielded 10c as a white powder(2.26 g, 4.9 mmol, 61%): mp 209-210° C.; IR (neat) λ_(max) 3298, 2952,2929, 2889, 2856, 1640, 1603, 1505, 1469, 1406, 1254, 1168, 1101, 1009,909, 833, 777, 733, 690, 505 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.81 (s,1H), 7.75 (d, J=8.7 Hz, 2H), 7.46 (d, J=8.8 Hz, 2H), 6.88 (d, J=8.6 Hz,2H), 6.81 (d, J=8.8 Hz, 2H), 0.99 (s, 9H), 0.98 (s, 9H), 0.22 (s, 6H),0.19 (s, 6H); ¹³C NMR (100 MHz, CDCl₃) δ 165.4, 159.0, 152.5, 131.9,128.9, 128.0, 122.0, 120.5, 120.3, 25.7, 25.7, 18.4, 18.3, 4.3, 4.3;LRMS (EI) m/z=457.3 [M]⁺.

4,4′-Sulfonyldiphenol was purchased from Alfa Aesar and used asreceived.

4,4′-Sulfonylbis(4,1-phenylene)disulfofluoridate (11a) was prepared from4,4′-sulfonyldiphenol following the general procedure for thepreparation of bis-fluorosulfate “AA” monomers. 11a was isolated aswhite powder (7.5 g, 91%): mp 118-122° C.; IR (neat) λ_(max) 1586, 1486,1451, 1405, 1324, 1291, 1231, 1178, 1139, 1103, 1015, 907, 850, 810,783, 688, 589, 574, 538, 509, 466 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.10(d, J=9.1 Hz, 4H), 7.53 (d, J=8.3 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ153.1, 141.3, 130.7, 122.5; ¹⁹F NMR (376 MHz, CDCl₃) δ 39.2; LRMS (EI)m/z=413.9 [M]⁺.

(4,4′-Sulfonylbis(4,1-phenylene)bis(oxy))bis(tert-butyldimethylsilane)(11c) was prepared from 4,4′-sulfonyldiphenol following the generalprocedure for the preparation of bis-silyl “BB” monomers, withsubstitution of tert-butyldimethylsilyl chloride with trimethylsilylchloride. 11c was isolated as a white powder (8.8 g, 92%): mp 135-137°C.; IR (neat) λ_(max) 2930, 2857, 1587, 1492, 1469, 1314, 1273, 1151,1105, 902, 838, 781, 757, 679, 645, 616, 574, 542 cm⁻¹; ¹H NMR (400 MHz,CDCl₃) δ 7.79 (d, J=8.8 Hz, 4H), 6.88 (d, J=8.8 Hz, 4H), 0.96 (s, 18H),0.2 (s, 12H); ¹³C NMR (100 MHz, CDCl₃) δ 160.0, 134.5, 129.6, 120.1,25.6, 18.3, −4.3; LRMS (EI) m/z=478.2 [M]⁺.

4,4′-(3-Oxo-1,3-dihydroisobenzofuran-1,1-diyl)bis(4,1-phenylene)disulfofluoridate(12a) was prepared from phenolphthalein following the general procedurefor the preparation of bis-silyl “BB” monomers, with substitution oftert-butyldimethylsilyl chloride with trimethylsilyl chloride. 12a wasisolated as a white solid: mp 93-98° C.; IR (neat) λ_(max) 1761, 1500,1443, 1410, 1288, 1229, 1139, 1081, 1016, 974, 938, 906, 846, 802, 753,691, 638, 571, 534, 503, 476 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.00 (ddd,J=0.8, 1.1, 7.7 Hz, 1H), 7.79 (td, J=1.2, 7.5 Hz, 1H), 7.65 (td, J=0.9,7.5 Hz, 1H), 7.57 (dt, J=0.8, 7.8 Hz, 1H), 7.47 (d, J=9.1 Hz, 4H), 7.35(dd, J=0.8, 9.1 Hz, 4H); ¹³C NMR (100 MHz, CDCl₃) δ 168.7, 150.4, 150.2,141.1, 135.0, 130.4, 129.4, 126.8, 125.4, 124.0, 121.5, 89.7; ¹⁹F NMR(376 MHz, CDCl₃) δ 37.9; LRMS (EI) m/z=489.1 [M]⁺.

3,5-Bis(tert-butyldimethylsilyloxy)benzoic acid was prepared by globalTBS protection of 3,5-dihydroxybenzoic acid, followed by selectiveliberation of the acid moiety as described by M. E. El-Khouly, E. S.Kang, K.-Y. Kay, C. S. Choi, Y. Aaraki, O. Ito, Chem. Eur. J. 2007, 13,2854-2863.

Butyl-3,5-bis(tert-butyldimethylsilyloxy)benzamide (13c). A 50 mL roundbottom flask equipped with a stirring bar and rubber septum was chargedwith 3,5-bis(tert-butyldimethylsilyloxy)benzoic acid (0.76 g, 2.0 mmol)and placed under argon. 15 mL dry DCM was added followed by the additionof hydroxybenzotriazole (HOBT; 0.3 g, 2.2 mmol) andN,N′-dicyclohexylcarbodiimide (DCC; 0.45 g, 2.2 mmol) in that order bypartial removal of the septum. The resulting slurry was stirred at roomtemperature for 10 min. Butan-1-amine (0.3 mL, 0.22 g, 3.0 mmol) wasthen added drop wise and the reaction mixture was stirred overnight. Theresulting heterogeneous solution was then filtered over a Buchner funneland the filtrate was further diluted with DCM and washed with 0.5 M HCl.The aqueous layer was extracted once more with DCM and the combinedorganics were dried over Na₂SO₄. The crude reaction mixture was thenconcentrated on to silica gel via rotary evaporation and subjected toflash chromatography (SiO₂, 10% EtOAc-hexanes; R_(f)=0.3 at 10%EtOAc-hexanes) to afford 13c as a white crystalline solid (0.76 g, 1.8mmol): mp 114-117° C.; IR (neat) λ_(max) 3294, 2929, 2857, 1632, 1583,1543, 1438, 1334, 1253, 1163, 1027, 1004, 935, 829, 778, 692, 667, 486cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 6.81 (d, J=2.1 Hz, 2H), 6.43 (t, J=2.1Hz, 1H), 6.02 (app s, 1H), 3.41 (q, J=7.1 Hz, 2H), 1.58 (p, J=7.7 Hz,2H), 1.39 (sex, J=7.2 Hz, 2H), 0.97 (s, 18H), 0.95 (t, J=7.3 Hz, 3H),0.19 (s, 12H); ¹³C NMR (100 MHz, CDCl₃) δ 167.3, 156.8, 137.1, 114.9,112.1, 39.9, 31.8, 25.8, 20.3, 18.3, 13.9, −4.3; LRMS (EI) m/z=437.3[M]⁺.

Biphenyl-4,4′-disulfonyl difluoride (14).Biphenyl-4,4′-disulfonylchloride (purchased from TCI chemicals; 5.0 g,0.014 mol) was dissolved in 40 mL acetonitrile and 5 mL water withstirring. To this mixture was added 4 eq. of saturated aqueous KHF₂ (1.2g). The reaction was allowed to proceed 3 hours. The mixture wasextracted twice with 30 mL ethyl acetate. The organic fractionscombined, washed with water, brine, and then dried over MgSO4. Solventwas removed under vacuum to provide 14 as a yellow solid (4.1 g, 90%):mp 194-197° C.; IR (neat) λ_(max) 1589, 1405, 1205, 1095, 816, 771, 750,709, 569, 535, 493 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.16 (d, J=8.5 Hz,4H), 7.88 (dd, J=0.7, 8.7 Hz, 4H); ¹³C NMR (100 MHz, CDCl₃) δ 145.9,133.4 (d, J=15.2 Hz), 129.4, 128.9; ¹⁹F NMR (376 MHz, CDCl₃) δ 66.1;LRMS (EI) m/z=318.0 [M]⁺.

Example 12 Catalyst screening by reaction of phenylfluorosulfate (15)and tert-butyldimethyl(p-tolyloxy)silane (16)

Experimental Setup:

A 0.5 M acetonitrile stock solution of the starting reagents wasprepared in the following manner: phenylfluorosulfate (15) (2.667 g,12.0 mmol), tert-butyldimethyl(p-tolyloxy)silane (16) (2.112 g, 12.0mmol) and diphenylmethane (standard, 0.403 g, 2.4 mmol) were dissolvedin enough dry acetonitrile to obtain 24 mL (combined mL) of stocksolution, which was subsequently placed under the atmosphere of argon.0.4 mL aliquots were parceled out into 1 mL scintillation vials, therebyproviding sixty individual 0.2 mmol reactions. Approximately 10 or 20mol % catalyst, as shown in Table 8, was then added to the reactionvials. The headspace was flushed with argon and the reaction mixtureswere shaken for 24 hrs at room temperature. Finally, 15 μL aliquots ofeach reaction mixture were diluted with 1 mL EtOAc and subjected toGC/MS endpoint analysis to determine the yield, if any, of phenyl tolylsulfate (17) and any byproduct 4-methylphenol (18). Calculated endpointsshown Table 8 were not confirmed by isolation and are considered“crude.” The percentages shown in Table 8 may vary by ±5% and are meantto serve as a general overview of the effective catalysts for thisreaction.

TABLE 8 Yield of Remaining Additional Catalyst (mol %)^(a) Prod. 17Materials^([c]) Starting Information  0. No Catalyst    0% 100% 15 100%16  1. 10% Triethylamine    0% 100% 15 100% 16  2. 10% DMAP    0% 100%15 100% 16  3. 10% Pyridine    0% 100% 15 100% 16  4. 10% DABCO    0%100% 15 100% 16  5. 10% 4-Cyanoqui-    0% 100% 15 100% 16 nuclidine  6.10% Imidazole    0% 100% 15 100% 16  7. 10% Proton Sponge    0% 100% 15100% 16  8. 10% n-Butyl amine  <1% <95% 15 >100% 16  9. 10% Piperidine ~5% <85% 15 >85% 16 Contains 18 (5%) and 19 10. 10% Benzimidazole    0%100% 15 100% 16 11. 10% K⁺OAc⁻    0% 100% 15 100% 16 12. 10%PhO⁻Na⁺•3H₂0  <1% <90% 15 100% 16 Contains 20 13. 20% NaOMe    0% 100%15 100% 16 14. 10% Na acetylacetate    0% 100% 15 100% 16 15. 10% Kphthalimide  >1% >95% 15 >95% 16 16. 20% KOH  >1% >95% 15 >95% 16 17.10% NaCN    0% 100% 15 100% 16 18. 10% NaN₃    0% 100% 15 100% 16 19.20% NaOH    0% 100% 15 100% 16 20. 10% BaOH•8H₂0    0% 100% 15 100% 1621. 10% KOtBu <20% ~80% 15 ~80% 16 22. 10% 1,2-  >1% >95% 15 >95% 16bis(methylamino)ethane 23. 10% 1,2-    0% 100% 15 100% 16diaminocyclohexane 24. 20% NaN(CN)₂    0% 100% 15 100% 16 25. 10% Na₂CO₃   0% 100% 15 100% 16 26. 10% K₃PO₄  <5% >90% 15 >95% 16 27. 10%CsF >90% <5% 15 <5% 16 28. 20% KF ~60% >30% 15 <20% 16 Contains 18 (5%)29. 10% TASF >90% <5% 15 <5% 16 30. 10% Bu₄N⁺F⁻ >90% <5% 15 <5% 16 31.10% Bu₄N⁺Cl⁻    0% 100% 15 100% 16 32.

~40% >50% 15 <5% 16 Contains 18 (25%) 33. 20% NaI    0% 100% 15 100% 1634. 10% PPh₃    0% 100% 15 100% 16 35. 20% PMe₂Ph    0% 100% 15 100% 1636. 10% DBU >95% 0% 15 0% 16 37. 10% DBN >95% <5% 15 <5% 16 38. 10%TMG >95% 0% 15 0% 16 39. 10% TBD >70% >25% 15 10% 16 Contains 18 (20%)40. 10% BEMP >95% 0% 15 0% 16 41. 10% t-Bu-P₄ >95% 0% 15 0% 16 42. 10%MeTBD >95% 0% 15 0% 16 43.

   0% >95% 15 <15% 16 Contains 18 (80%) 44.

   0% 100% 15 <5% 16 Contains 18 (95%) 45.

~80% <20% 15 <5% 16 Contains 18 (10%) 46. 20% Et₄N⁺OH⁻ ~20% >55% 15 <20%16 Contains 18 (45%) 47. 20% NaBF₄    0% 100% 15 100% 16 48. 10%TiCl₄•2THF    0% 100% 15 >70% 16 Contains 18 (25%) 49. 10% SnCl₂•2H₂0   0% 100% 15 <5% 16 Contains 18 (95%) 50. 10% BF₃•OEt₂    0% 100% 15<5% 16 Contains 18 (90%) 51. 10% ZnCl₂    0% 100% 15 100% 16 52. 10%ZnBr₂    0% 100% 15 100% 16 53. 10% AlEt₃    0% 100% 15 100% 16 54. 10%Et₂AlCl    0% 100% 15 100% 16

In Table 8, the catalyst amount was measured as close as practicallypossible to 10 or 20 mol %. The percentage of product in the crudereaction mixture was calculated from a molarity-based calibration curvederived from compound 17. Yield may vary by ±5%. The remaining startingmaterial percentage was derived from the initial reaction mixtureconcentration in reference to diphenylmethane (internal standard).Actual yield of 15 and 16 may vary by ±5%. Percentage of 4-methylphenol18 is in reference to starting material 16, i.e. actual yield of 18 mayvary by ±5%. In some cases the observed product was the mixed sulfateester/sulfamoyl derivative of phenol and piperidine (Compound 19), ordiphenylsulfate 20.

Example 13 Comparison of the Present Polymerization Method to the Methodof Firth (U.S. Pat. No. 3,733,304) for Preparation of Poly(Bisphenol ASulfate)

Poly(bisphenol A sulfate) was prepared by the method of Firth (U.S. Pat.No. 3,733,304), i.e., by reaction of disodium bisphenol A with bisphenolA-bisfluorosulfate in chlorobenzene at about 150 to 165° C. Theresulting product was precipitated into water as described by Firth, andthen analyzed by GPC relative to polystyrene standards, as describedherein. The GPC trace is shown in Panel A of FIG. 15. The polydispersityof the polymer prepared according to the Firth method was about 6 whenintegrated with the cyclic oligomer peak at about 22 minutes elutiontime. For comparison, a GPC of poly(bisphenol A sulfate) from the largescale preparation in Example 1 herein, prepared according to the presentinvention, is shown in Panel B of FIG. 15. As is evident from the twoGPC traces in the present method provides a higher molecular weightproduct with a much narrower polydispersity and significantly lesscyclic oligomeric byproduct.

Example 14 Stability of Poly(Bisphenol A Sulfate) to Various ProcessingConditions

Poly(bisphenol A sulfate) was prepared under bulk, solventlessconditions (neat melt of monomers 2a and 2c, with no solvent using 1%BEMP catalyst at 120° C.) at 2 mmol, 20 mmol and 250 mmol scales. Thepolymer samples were dissolved in DMF and GPC traces of these materialswere compared to a redissolved sample of the thin film from Example 5(made from the large scale polymer of Example 1). The GPC traces areshown in FIG. 16, and clearly show that the polymers havingsubstantially the same molecular weight profile were obtained at eachscale. It is also evident that processing the polymer into a film didnot significantly affect the molecular weight profile. In addition, asample of the large scale polymer from Example 1 was heated with a heatgun for a prolonged period, and another sample was heated and forcedthrough a 0.45 micron filter, neither of which significantly affectedthe molecular weight profile of the samples (see FIG. 16).

Example 15 Preparation of Poly(Bisphenol A Sulfate) fromBis-Silyl-Bisphenol A and Sulfuryl Fluoride

A 100 mL Schlenk flask containing a ground glass stopcock, equipped witha stirring bar and a rubber septum, was flame-dried under vacuum (7 mmHg). Upon cooling to room temperature, the reaction vessel was weighed(sans an internal atmosphere), charged with sulfuryl fluoride gas(SO₂F₂) and finally re-weighed to determine the quantity of SO₂F₂ (752mg, 7.37 mmol).((Propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(tert-butyldimethylsiane)(3.30 g, 7.22 mmol) dissolved in 7 mL anhydrous DMF and2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine(BEMP; 368 μL, 101 mg, 0.368 mmol) as a 1 M solution in hexanes werethen added to the reaction vessel in that order and the resultingmixture was stirred at room temperature for 20 min, as a closed (to theatmosphere) system. The reaction vessel was then placed in a 150° C. oilbath and shortly thereafter the evolution of low boiling solvents(presumably hexanes and tert-butylfluorodimethylsilane (TBSF)) wasvisible on walls of the reaction vessel. The reaction progressed as aclosed system at 150° C. for 30 min at which point the stopcock wasopened thereby releasing gaseous hexanes and TBSF, heating was thencontinued for an additional 2 h as an open system. The reaction mixturewas then removed from the oil bath as a viscous, slightly yellow clearliquid and allowed to cool to room temperature. Direct addition of thereaction mixture to 200 mL MeOH resulted in precipitation ofBPA-polysulfate as a white fibrous solid. Drying under vacuum at 80° C.for 3 h yielded 1.966 g (94%) with M_(n) of 95,000 Da based onpolystyrene standards.

Example 16 Fluorosulfonyl Monomers Prepared from Primary Amines byReaction with Ethylene Sulfonylfluoride (ESF)

FIG. 17, Panel A, illustrates a facile synthesis ofbis(2-fluorsulfonylethyl)amines by reaction of primary amines with ESFin DCM or acetic acid. Panel B of FIG. 17 illustrates four examples ofsuch monomers prepared in this manner. FIG. 17, Panel C, illustratessome examples of polymers prepared from these monomers and abis-silyl-bisphenol A monomer.

General Procedure for the Reaction of ESF with Primary and SecondaryAmines.

Starting amine (1 equiv.) was dissolved in DCM (about 0.1 to 0.5 M insubstrate) and treated with ESF (about 1 to 2.5 equiv.) following aprocedure adapted from Hyatt et al. (J. Org. Chem., 1979, 44:3847-3858).The reaction mixture was stirred at room temperature for several minutesto an hour, monitoring conversion by LCMS. Upon completion, DCM andexcess of ESF were removed using rotary evaporator and dried, providingproduct virtually free of any impurities. In certain cases columnchromatography can be used to obtain analytically pure samples of ESFadducts.

2,2′-((2-(1H-Indol-3-yl)ethyl)azanediyl)diethanesulfonyl fluoride

Following the general procedure described above with an 2 equivalents ofESF and stirring the reaction mixture at room temperature for 3 hoursafforded an analytically pure sample was obtained by flash columnchromatography (hexane/EtOAc—9/1 to 6/4). Product was obtained as yellowoil in quantitative yield (1.9 g). ¹H NMR (400 MHz, CDCl₃) δ (ppm): 8.04(s, 1H), 7.57 (d, J=7.8 Hz, 1H), 7.37 (d, J=7.9 Hz, 1H), 7.23 (t, J=7.5Hz, 1H), 7.16 (t, J=7.4 Hz, 1H), 7.01 (br s, 1H), 3.48-3.39 (m, 4H),3.15-3.05 (m, 4H), 2.96-2.89 (m, 2H), 2.89-2.80 (m, 2H); ¹³C NMR (101MHz, CDCl₃) δ (ppm): 136.3, 127.1, 122.3, 122.2, 122.1, 119.6, 118.5,113.0, 111.5, 54.2, 49.4 (d, J=13.2 Hz), 47.9, 23.3; ¹⁹F NMR (376 MHz,CDCl₃) δ (ppm): +57.9; R_(f) (hexane/EtOAc—7/3): 0.27; ESI-MS (m/z): 381[MH]⁺.

2,2′-((Furan-2-ylmethyl)azanediyl)diethanesulfonyl fluoride

Following the general procedure described above in DCM (0.33 M) inpresence of 2 equiv. of ESF afforded a crude product, which was purifiedby column chromatography (hexane/EtOAc—95/5 to 7/3). Product wasobtained as yellow oil in 99% yield (1.6 g). ¹H NMR (400 MHz, CDCl₃) δ(ppm): 7.41 (dd, J=1.9, 0.8 Hz, 1H), 6.37 (dd, J=3.2, 1.9 Hz, 1H), 6.28(dd, J=3.2, 0.7 Hz, 1H), 3.81 (s, 2H), 3.53 (td, J=6.9, 3.6 Hz, 4H),3.16 (td, J=7.0, 1.2 Hz, 4H); ¹³C NMR (101 MHz, CDCl₃) δ (ppm): 149.9,143.1, 110.7, 110.1, 49.6, 49.4 (d, J=11.1 Hz), 47.9; ¹⁹F NMR (376 MHz,CDCl₃) δ (ppm): +57.9; R_(f) (hexane/EtOAc—7/3): 0.47; ESI-MS (m/z): 340[MNa]⁺.

2,2′-((3-Ethynylphenyl)azanediyl)diethanesulfonyl fluoride (adapted fromHyatt et al. J. Org. Chem., 1979, 44:3847-3858): ESF (1.8 mL; 20 mmol)was added to aniline (1.17 g; 10 mmol) in glacial acetic acid (3 mL) andreaction mixture was stirred at 50° C. for 24 hrs. Upon completion,crude product was isolated by filtration, washed with hexanes andrecrystallized from CCl₄-DCM. Product was obtained as light browncrystals in 87% yield (2.94 g). m.p. 98-100° C. ¹H NMR (400 MHz, CDCl₃)δ (ppm): 7.31 (t, J=8.0 Hz, 1H), 7.10-7.06 (m, 1H), 6.85-6.82 (m, 1H),6.78-6.73 (m, 1H), 4.01 (t, J=6.4 Hz, 4H), 3.67-3.59 (m, 4H), 3.10 (s,1H); ¹³C NMR (101 MHz, CDCl₃) δ (ppm): 144.0, 130.5, 124.3, 124.2,117.6, 115.0, 83.3, 78.0, 48.3 (d, J=14.4 Hz), 46.8; ¹⁹F NMR (376 MHz,CDCl₃) 6 (ppm): +57.2; ESI-MS (m/z): 338 [MH]⁺.

General Procedure for the Reaction of ESF with Sulfonamides andAlcohols:

Starting material (1 equiv.) and triphenylphosphine (0.1 equiv.) weredissolved in DCM (0.33M in substrate) and treated with ESF (about 1 to2.5 equiv.). Reaction mixture was stirred at room temperature overnight,monitoring conversion by LCMS/GCMS/TLC. Upon completion, DCM and anexcess of ESF were removed using rotary evaporator and crude product waspurified by short column chromatography.

Following the general procedure for reaction of ESF with sulfonamides,2-(4-Methyl-N-(prop-2-yn-1-yl)phenylsulfonamido)ethanesulfonyl fluoridewas obtained as a white solid in 78% yield (251 mg). R_(f)(hexane/EtOAc—5/1): 0.25; m.p. 125-126° C.; ¹H NMR (400 MHz, CDCl₃) δ(ppm): 7.74 (d, J=8.3 Hz, 2H), 7.35 (d, J=8.5 Hz, 2H), 4.15 (d, J=2.5Hz, 2H), 3.87-3.80 (m, 2H), 3.71-3.65 (m, 2H), 2.45 (s, 3H), 2.19 (t,J=2.5 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ (ppm): 144.8, 134.5, 130.1,127.9, 76.2, 75.0, 50.4 (d, J=16.0 Hz), 41.9, 38.8, 21.8; ¹⁹F NMR (376MHz, CDCl₃) δ (ppm): 55.9; ESI-MS (m/z): 320 [MH]⁺.

Following the general procedure for reaction of ESF with sulfonamides,2,2′-(((4-(3-Phenyl-5-(trifluoromethyl)-1H-pyrazol-1-yl)phenyl)sulfonyl)azanediyl)-diethanesulfonylfluoride was obtained as a white solid in 60% yield (175 mg). R_(f)(hexane/EtOAc—5/1): 0.21; m.p. 135-137° C.; ¹H NMR (400 MHz, CDCl₃) δ(ppm): 7.84 (d, J=8.6 Hz, 2H), 7.58 (d, J=8.6 Hz, 2H), 7.47-7.43 (m,1H), 7.43-7.39 (m, 1H), 7.28-7.23 (m, 3H), 6.80 (s, 1H), 3.86-3.80 (m,4H), 3.71-3.66 (m, 4H); ¹³C NMR (101 MHz, CDCl₃) δ (ppm): 145.4, 144.8(d, J=38.3 Hz), 143.9, 135.7, 130.0, 129.4, 129.0, 128.8, 128.6, 117.4(d, J=336.3 Hz), 107.2, 50.7, 50.6 (d, J=16.1 Hz), 45.6; ¹⁹F NMR (376MHz, CDCl₃) δ (ppm): +59.4, −62.8; ESI-MS (m/z): 588 [MH]⁺.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

1: A polymerization method comprising the step of contacting a liquidmonomer composition with a basic catalyst, wherein the monomercomposition comprises at least one compound of formula F—X—F and atleast one compound of formula (R¹)₃Si—Z—Si(R¹)₃; wherein: each R¹independently is a hydrocarbyl group; X has the formula -A(-R²-A)n-;each A independently is SO₂, C(═O), or Het; R² comprises a first organicmoiety; n is 0 or 1; Het is an aromatic heterocycle comprising at leasttwo carbon atoms and at least one nitrogen atom in a heteroaromatic ringthereof, and when A is Het, the F substituent is attached to a carbonatom of the heteroaromatic ring thereof; Z has the formula -L-R³-L-;each L independently is O, S, or N(R⁴); R³ comprises a second organicmoiety; each R⁴ independently is H or a third organic moiety; andwherein the F and (R¹)₃Si substituents form a silyl fluoride byproductof formula (R¹)₃Si—F as the respective A and L groups of the monomerscondense to form an X—Z polymer chain; and wherein the basic catalystcomprises at least one material selected from the group consisting of anamidine, a guanidine, a phosphazene, a nitrogen heterocyclic carbene, atertiary alkoxide, and a fluoride salt. 2: The method of claim 1wherein: each R¹ independently is an alkyl or aryl group; X has theformula -A(-R²-A)n-; each A is SO₂; R² comprises a first organic moiety;n is 0 or 1; Z has the formula -L-R³-L-; each L independently is O; andR³ comprises a second organic moiety comprising at least one aryl orheteroaryl group directly bonded to each L. 3: The method of claim 1wherein the n is
 0. 4: The method of claim 1 wherein Het is a1,3,5-triazine. 5: The method of claim 1 wherein the monomer compositionincludes a compound in which X includes an additional F substituent on asulfonyl, carbonyl, or heteroaryl activating group, A, such that theadditional F substituent also reacts with a (R¹)₃Si substituent on anoxygen, sulfur or nitrogen atom linking group, L, to form a silylfluoride, and the activating group condenses with the linking group tointroduce a branch point in the polymer. 6: The method of claim 1wherein the monomer composition includes a compound in which Z includesan additional silyl substituent, (R¹)₃Si, on an oxygen, sulfur ornitrogen atom linking group, L, such that the additional silylsubstituent also reacts with a F substituent on a sulfonyl, carbonyl, orheteroaryl activating group, A, to form a silyl fluoride and the linkinggroup condenses with the activating group to introduce a branch point inthe polymer. 7: The method of claim 1 wherein n is 1; R² is -L¹-R⁵-L¹-;each L¹ independently is selected from the group consisting of O, S, andN(R⁴); and each R⁴ independently is H or the third organic moiety, andR⁵ comprises an organic moiety. 8: The method of claim 1 wherein n is 1;R² is -L¹-R⁵—; L¹ is selected from the group consisting of O, S, andN(R⁴); R⁴ s H or the third organic moiety; and R⁵ is an organic moiety.9: The method of claim 1 wherein the basic catalyst comprises1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). 10: The method of claim 1wherein the basic catalyst comprises at least one phosphazene selectedfrom the group consisting of2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine(BEMP) and1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ⁵,4λ⁵-catenadi(phosphazene)(P₄-t-Bu). 11: The method of claim 1 wherein the basic catalystcomprises at least one fluoride salt selected from the group consistingof CsF, CsFHF, KF, tetrabutylammonium fluoride (TBAF), andtris(dimethylamino)sulfonium-difluorotrimethylsilicate (TASF). 12: Themethod of claim 1 wherein the basic catalyst comprises at least oneguanidine selected from the group consisting of1,1,3,3-tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD), and 7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene (MTBD). 13: Themethod of claim 1 wherein the basic catalyst comprises at least onenitrogen-heterocyclic carbene selected from the group consisting of animidazole-2-ylidene, a 1,2,4-triazole-5-ylidene, a thiazole-2-ylidene,and an imidazolin-2-ylidene. 14: The method of claim 1 wherein each A isSO₂. 15: The method of claim 1 wherein each R² comprises an aryl orheteroaryl moiety either directly bonded to an A group or bonded to Avia an oxygen atom attached to the aryl or heteroaryl moiety. 16: Themethod of claim 1 wherein the polymer comprises a polymeric chainrepresented by a formula selected from the group consisting of:(-A(-R²-A)n-L-R³-L)x-;  Formula (I):(-A-R²-A-L-R³-L)y-;  Formula (II):(-A-L¹-R⁵-L¹-A-L-R³-L)z-;  Formula (III):(-A-L¹-R⁵-A-L-R³-L)m-;  Formula (IV):(-A-L-R³-L)p-; and  Formula (V):(-A-R²-A-L-R³-L)a-(-A-L¹-R⁵-L¹-A-L-R³-L)b-(A-L¹-R⁵-A-L-R³-L)c-(-A-L-R³-L)d-;  Formula(VI): wherein: each A independently is SO₂, C(═O), or Het; each L and L¹independently is O, S, or N(R⁴); each R² and R⁵ independently comprisesa first organic moiety; each R³ comprises a second organic moiety; eachR⁴ independently is H or a third organic moiety; each n independently is0 or 1; each Het independently is an aromatic heterocycle comprising atleast two carbon atoms and at least one nitrogen atom in aheteroaromatic ring thereof, and when A is Het, the F substituent isattached to a carbon atom of the heteroaromatic ring thereof; each of x,y, z, m, and p is the average number of repeating units in the polymerand has a value of at least 10; and each of a, b, c, and d is theaverage number of respective repeating units, and independently can be 0or greater, provided the sum of a, b, c, and d is at least
 10. 17: Themethod of claim 1 wherein one or more of the R², R³, R⁴, and R⁵,comprises a moiety selected from the group consisting of a hydrocarbon,a heterocycle, a carbohydrate, an amino acid, a polypeptide, a peptideanalog, and a combination of two or more thereof. 18: The method ofclaim 1 wherein one or more of R¹, R², R³, R⁴, and R⁵ is substituted byat least one substituent selected from the group consisting of hydroxyl,halogen, nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂, —CN, —SO_(v)R⁶,—SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂,—N(R⁶)OR⁶, —N(R⁶)C(O)R, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂,—OC(O)OR⁶, azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy,fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy),alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, anamino acid, and a polypeptide; wherein each R⁶ independently is H,alkyl, or aryl, and v is 0, 1, or
 2. 19: The method of claim 1 whereinthe monomer composition comprises (a) two or more different compounds offormula F—X—F, (b) two or more different compounds of formula(R¹)₃Si—Z—Si(R¹)₃, or (c) c combination of both (a) and (b). 20: Themethod of claim 19 wherein the two or more different compounds offormula (R¹)₃Si—Z—Si(R¹)₃ differ by the selection of R¹, Z, or both R¹and Z. 21: The method of claim 1 wherein the monomer compositioncomprises at least one compound of Formula VII and at least one compoundof Formula VIII:

wherein each R¹ independently is an alkyl or aryl group, and each R⁹independently is a covalent bond, C(CH₃)₂, C(CF₃)₂, or SO₂. 22: Themethod of claim 1 wherein the liquid monomer mixture comprises a mixtureof the monomers dissolved in a solvent. 23: The method of claim 1wherein the liquid monomer mixture comprises a melted mixture of themonomers. 24: The method of claim 1 wherein the F—X—F monomer comprisessulfuryl fluoride (FSO₂F). 25: The method of claim 1 wherein the F—X—Fmonomer comprises a bisfluorosulfonyl monomer of formulaF—SO₂—CH₂CH₂—N(R¹)—CH₂CH₂—SO₂—F, wherein R¹¹ comprises an organicmoiety. 26: The method of claim 25 wherein R¹¹ comprises a moietyselected from the group consisting of a hydrocarbon, a heterocycle, acarbohydrate, an amino acid, a polypeptide, a peptide analog, and acombination of two or more thereof. 27: The method of claim 25 whereinR¹¹ is substituted by at least one substituent selected from the groupconsisting of hydroxyl, halogen, nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂,—CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶,—N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂,—OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl, alkenyl, alkynyl,alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl,poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, acarbohydrate, an amino acid, and a polypeptide; wherein each R⁶independently is H, alkyl, or aryl, and v is 0, 1, or
 2. 28: A polymercomprising a polymeric chain having a formula selected from the groupconsisting of:(-A(-R²-A)n-L-R³-L)x-;  Formula (I):(-A-R²-A-L-R³-L)y-;  Formula (II):(-A-L¹-R⁵-L¹-A-L-R³-L)z-;  Formula (III):(-A-L¹-R⁵-A-L-R³-L)m-;  Formula (IV):(-A-L-R³-L)p-; and  Formula (V):(-A-R²-A-L-R³-L)a-(-A-L¹-R⁵-L¹-A-L-R³-L)b-(A-L¹-R⁵-A-L-R³-L)c-(-A-L-R³-L)d-;  Formula(VI): wherein: each A independently is SO₂, C(═O), or Het; each L and L¹independently is O, S, or N(R⁴); each R² and R⁵ independently comprisesa first organic moiety; each R³ comprises a second organic moiety; eachR⁴ independently is H or a third organic moiety; each n independently is0 or 1; each Het independently is an aromatic heterocycle comprising atleast two carbon atoms and at least one nitrogen atom in aheteroaromatic ring thereof, and when A is Het, the F substituent isattached to a carbon atom of the heteroaromatic ring thereof; each of x,y, z, m, and p is the average number of repeating units in the polymerand has a value of at least 10; and each of a, b, c, and d is theaverage number of respective repeating units, and independently can be 0or greater, provided the sum of a, b, c, and d is at least 10; and thepolymer includes a group of formula E-A- at one or both ends of thepolymer chain, wherein each E independently is fluoro, OR⁸, NHR⁸,N(R⁸)₂, azido, CN, or SR⁸, and each R⁸ independently is an organicmoiety. 29: The polymer of claim 28 wherein one or more of the organicmoieties R², R³, R⁴, R⁵ and R⁸ is selected from the group consisting ofa hydrocarbon, a heterocycle, a carbohydrate, an amino acid, apolypeptide, a peptide analog, and a combination of two or more thereof.30: The polymer of claim 28 wherein one or more of R², R³, R⁴, R⁵ and R⁸is substituted by at least one substituent selected from the groupconsisting of hydroxyl, halogen, nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂,—CN, —SO_(v)R⁶, —SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶,—N(R⁶)₂, —N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂,—OC(O)N(R⁶)₂, —OC(O)OR⁶, azido, alkyl, cycloalkyl, alkenyl, alkynyl,alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl,poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, acarbohydrate, an amino acid, and a polypeptide; wherein each R⁶independently is H, alkyl, or aryl, and v is 0, 1, or
 2. 31: The polymerof claim 28, wherein the polymer comprises a compound of Formula IX:

wherein t is the average number of monomer units and is at least 10,each E independently is fluoro, OR⁸, NHR⁸, N(R⁸)₂, azido, CN, or SR⁸,and each R⁸ independently is an organic moiety. 32: The polymer of claim28 wherein the polymer has the Formula (I): (-A(-R²-A)n-L-R³-L)x-, inwhich each A is SO₂, and each R² independently is—CH₂CH₂—N(R¹¹)—CH₂CH₂—, wherein R¹¹ comprises an organic moiety. 33: Thepolymer of claim 32 wherein R¹¹ comprises a moiety selected from thegroup consisting of a hydrocarbon, a heterocycle, a carbohydrate, anamino acid, a polypeptide, a peptide analog, and a combination of two ormore thereof. 34: The polymer of claim 32 wherein R¹¹ is substituted byat least one substituent selected from the group consisting of hydroxyl,halogen, nitro, —C(O)R⁶, —C(O)OR⁶, —C(O)N(R⁶)₂, —CN, —SO_(v)R⁶,—SO_(v)N(R⁶)₂, R⁶SO_(v)N(R⁶)—, —N(R⁶)SO_(v)R⁶, —SO₃R⁶, —N(R⁶)₂,—N(R⁶)OR⁶, —N(R⁶)C(O)R⁶, —N(R⁶)C(O)OR⁶, —N(R⁶)C(O)N(R⁶)₂, —OC(O)N(R⁶)₂,—OC(O)OR⁶, azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy,fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy),alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, anamino acid, and a polypeptide; wherein each R⁶ independently is H,alkyl, or aryl, and v is 0, 1, or
 2. 35: The polymer of claim 28 whereinthe polymer has a molecular weight polydispersity index (PDI) of lessthan about 2.2 based on gel permeation chromatography using polystyrenestandards, and includes less than about 5 percent by weight of cyclicoligomers. 36: The polymer of claim 35 wherein the polymer ispoly(bisphenol A sulfate). 37: A transparent, substantially colorlessfilm or sheet comprising poly(bisphenol A sulfate). 38: A method ofpreparing the film or sheet of claim 37 comprising pelletizingpoly(bisphenol A sulfate) into pellets, and consolidating the pellets atan elevated pressure and at a temperature greater than the glasstransition temperature thereof. 39: The method of claim 38 wherein theelevated pressure is at least about 25,000 pounds-per-square inch (psi)and the temperature is in the range of about 200 to 250° C.